Manual method for injection molding coated components

ABSTRACT

Described herein is a manual process for injection molding of coated components, more particularly coated soles of plastic, where first of all the molding tool is lined with a release agent composition and, after flashing of this release agent composition, a composition for forming the component is injected. After crosslinking of these two compositions, the produced coated component is removed from the molding tool and subjected optionally to an aftertreatment.

FIELD OF INVENTION

The present invention relates to a manual process for injection moldingof coated components, more particularly coated soles of plastic, whereinfirst of all the molding tool is lined with a release agent compositionand, after flashing of this release agent composition, a composition forforming the component is injected. After crosslinking of these twocompositions, the coated component produced is removed from the moldingtool and subjected optionally to an aftertreatment.

BACKGROUND

A wide variety of different components with variable layer thicknessesare nowadays mostly produced by means of the injection molding method.Certain materials, especially low-density foams, are unsuited toproducing components, however, since they may exhibit problems inrelation to propensity toward soiling, UV stability, and defect-freeprocessing. Particularly in the area of the production of footwear solesor in the area of the furniture industry, however, there is a sustaineddemand for components of this kind for producing footwear or upholsteredfurniture. One way of endowing such components with enhanced protectionis by coating. The coating must on the one hand have effective adhesionon the component, but on the other hand must be sufficiently flexibleand elastic to allow the coated components to be employed even in areasinvolving high mechanical stressing.

The components are usually coated at present after they have beenproduced, in an overmolding process, for example, or by subsequentlacquering processes. Such processes, however, are inefficient, sincethey necessitate a further process step after production. Moreover,prior to further coating with a basecoat, for example, or to adhesivebonding to other components, it is necessary to remove the externalrelease agent used when producing the components, and permittingdemolding of the components from the molding tool without damage; suchremoval entails costly and inconvenient cleaning processes. Furthermore,the tools used must also be subjected to ongoing cleaning.

Further disadvantages associated with the use of external mold releaseagents include a frequent lack of compatibility between release agentand the composition used for producing the component, and/or betweenrelease agent and molding tool, leading to adhesion problems. Whenexternal release agents are used, moreover, there is an increase in thecost and complexity of the process and hence in the operating times.Furthermore, the use of external release agents leads frequently toshiny surfaces on the components produced, this being unwantedespecially in the footwear industry. Especially when using foams inorder to produce components, furthermore, irregular surface structures,especially rough surface structures and also those in some cases havingexposed fibers or pores, are obtained, and cannot be entirely eliminatedeither by using an external release agent or by means of subsequentcoating with the layers of coating—in general, surfacer coats,basecoats, and clearcoats.

An advantage, accordingly, would be a manual process for producingcoated components wherein coating takes place during the actualproduction of the component and wherein, moreover, there is no need forthe use of external release agents. However, despite the absence ofexternal release agents, it ought to be possible to demold the coatedcomponents without damage. Furthermore, the coated components producedby this process ought not to have an irregular surface. Furthermore,with the manual process, it ought also to be possible to producecomponents of complex geometry without any defects occurring.Additionally, without costly and inconvenient cleaning and/or grindingsteps, it ought to be possible to recoat the coated components produced,using commercial basecoat and clearcoat materials, and/or to bond themusing adhesives.

Problem and Solution

A problem for the present invention to address, accordingly, was that ofproviding a manual process for injection molding of coated components,more particularly soles of plastic, which permits short operating timesand also damage-free demolding and in which the coated componentsproduced can be recoated without costly and inconvenient cleaning and/orgrinding steps, using commercial basecoat and clearcoat materials,and/or can be bonded using adhesives. Furthermore, the surface of thecoated components produced ought not to exhibit any irregularities.Moreover, both the mechanical properties and the resistance of thecoated components produced toward environmental influences ought to beimproved. The manual process ought also, furthermore, to allow theproduction of components of complex geometry without any defectsoccurring.

Solution to the Problem

It has been found that the stated problems have been solved by a newmanual process for injection molding of coated components, moreparticularly soles of plastic, comprising the following steps in theorder indicated:

-   -   (A) application of a release agent composition to at least one        inside of at least one molding part of a closable molding tool,    -   (B) flashing of the release agent composition applied in step        (A),    -   (C) optional insertion of at least one material M1 and heating        of the molding tool,    -   (D) application of a composition Z1 into the opened molding        tool,    -   (E) manual closing of the molding tool,    -   (F) crosslinking of the release agent composition and also of        the composition Z1 applied in process step (D),    -   (G) optional application of at least one further composition Z2        and crosslinking of said composition(s),    -   (H) manual opening of the molding tool,    -   (I) manual removal of the molded coated component, and    -   (J) optional aftertreatment of the molded coated component,        where the release agent composition comprises:    -   (a) at least one solvent L,    -   (b) at least one compound of the general formula (I)

R¹—(C═O)_(r)—O-(AO)_(s)—R²   (I)

-   -   -   in which R¹ is a saturated or unsaturated, aliphatic            hydrocarbon radical having 6 to 30 carbon atoms,        -   R² is H, a PO(OH)₂ radical, or the optionally partially            phosphated radical of a monosaccharide or disaccharide, or            the optionally partially phosphated radical of an alditol,        -   AO stands for one or more alkylene oxide radicals selected            from the group consisting of ethylene oxide, propylene oxide            and butylene oxide,        -   r is 0 or 1, and s is 0 to 30;

    -   (c) optionally at least one polyether-modified        alkylpolysiloxane,

    -   (d) at least one polysiloxane of the general formula (II)

R³—Si(R⁴)₂—[O—Si(R⁴)(R⁵)]_(a)—[O—Si(R⁴)₂]_(b)—O—Si(R⁴)₂—R³   (II),

-   -   -   in which        -   R³ and R⁴, in each case independently of one another, are a            methyl group or a (HO—CH₂)₂—C(CH₂—CH₃)—CH₂—O—(CH₂)₃—.            radical,        -   R⁵ is a methyl group,        -   a is 0 or 1 to 10, and        -   b is 3 to 30; and

    -   (e) optionally at least one binder B.

The above-stated process is also referred to below as the process of theinvention and, accordingly, is the subject of the present invention.Preferred embodiments of the process of the invention are evident fromthe description hereinafter and also from the dependent claims.

Because of the short flashing and crosslinking times, the release agentused in the process of the invention not only allows short operatingtimes but also leads to damage-free demolding of the coated componentsproduced. This release agent, moreover, exhibits high adhesion to thecomponent produced and permits aftercoating with commercial basecoat andclearcoat materials, and/or adhesive bonding, without costly andinconvenient cleaning and/or grinding steps. Even without aftercoating,the coating obtained on the component by the release agent is highlyelastic or flexible and also UV-stable and exhibits a consistent degreeof gloss or mattness, thus resulting not only in damage-free demoldingof the coated component but also in effective protection of the coatedcomponent produced with respect to environmental influences, such as UVradiation, dirt or the like, as early as immediately after production,in other words without further treatment of the component. Moreover, thecoated components produced have a regular surface even when producedusing foams which, in combination with conventional release agents, leadto components having a highly irregular surface. Furthermore, it hasalso been possible to produce components having complex geometries,examples being footwear soles and also components with struts a fewmillimeters wide, without defects. Since only small residues of therelease agent remain in the molding tool, the molding tools used do nothave to be cleaned before every further application of the releaseagent.

DETAILED DESCRIPTION

Definitions:

First of all a number of terms used in the context of the presentinvention will be elucidated.

The process of the invention is a manual process. This means, in thecontext of the present invention, that said process is not tied tostrict cycle times for each process step. Accordingly, there is markedvariation in the timespan needed in order to carry out each process stepduring multiple repetition of the process. This means, therefore, thatin the case of dual repetition of the process, for example, on oneoccasion one minute and on one occasion 5 minutes may be needed forprocess step (C). Manual processes within the meaning of the presentinvention therefore do not cover processes in which the individualprocess steps are tied to strict cycle times, in other words where, onmultiple repetition of the process, the timespan which must be observedmust always be exactly the same for a process step or the variation inthe timespan must only be very minimal.

However, the term “manual process” in the sense of the present inventiondoes not mean that such processes cannot include automated processsteps, an example being the use of robots. The factor governing whethera process is or is not to be understood as manual process within themeaning of the present invention is therefore solely the process regimewithout a tie to strict cycle times.

A component in accordance with the invention means an individual partwhich, joined with other components, forms an assembly. If, therefore,the component is part of a bodywork, of a motor vehicle, for example, itcan be assembled with other bodywork components to form a bodywork.Where, for example, the component is a footwear sole, it can beassembled with other components of a footwear item to form such an item.In general, however, independently of the purpose of the material asbeing able to serve as a component, the invention relates generally tothe production of coated components and is therefore not limited tocomponents in the above sense. Consequently, where reference is madebelow to the coating of components, this also generally embraces thecoating of materials without a “component” function; in other words,such materials need not necessarily be used as a component for producingassemblies.

A coated component in accordance with the invention means a componentwhich has a coating on the surface. In accordance with the invention,the coating is applied to the surface of the component by crosslinkingof the release agent composition during the production of saidcomponent. The coating of the component, accordingly, concerns thecrosslinked release agent composition.

The term “inside” refers in accordance with the invention to the surfaceof a molding part of a molding tool that comes into contact with therelease agent composition and also with the composition Z1 and,optionally, further materials and compositions used in the process,during the production of the component.

In process step (B) of the process of the invention, the applied releaseagent composition is flashed. This means, in accordance with theinvention, the active or passive evaporation of solvents in the releaseagent, usually at a temperature which is higher than the ambienttemperature and which is 40 to 90° C. for example. During flashing,therefore, solvents present in the applied release agent undergoevaporation. The release agent is able to run during flashing, becauseit is still fluid at any rate directly after application and at thestart of flashing. This is because at least a release agent applied byspraying is generally applied in droplet form and not in uniformthickness. As a result of the solvents present, however, the releaseagent is fluid and is therefore able to run to form a uniform, smoothcoating film. At the same time, solvents undergo successive evaporation,and so the coating layer resulting from the flashing phase iscomparatively smooth and comprises less solvent than the applied releaseagent. The release agent layer after flashing, however, is not yet inthe ready-to-use state. While it is indeed, for example, no longerfluid, it is still soft or tacky, and may have undergone only partialdrying. In particular, the release agent layer is not yet crosslinked,as described later on below.

The term “poly(meth)acrylate” refers both to polyacrylates and topolymethacrylates. Poly(meth)acrylates may therefore be composed ofacrylates and/or methacrylates and may comprise further ethylenicallyunsaturated monomers such as styrene or acrylic acid, for example.

The term “aliphatic radical” refers herein to a radical of an acyclic orcyclic, saturated or unsaturated carbon compound, this radicalcontaining no aromatic structures. Aliphatic radicals may accordingly,however, contain heteroatoms, such as oxygen or nitrogen, for example.

In process step (F) and optionally (G), the release agent composition,the composition Z1, and any further compositions are crosslinked. Thisrefers to the curing of these compositions, in other words theconversion of these compositions into the ready-to-use state, meaning astate in which the component furnished with the release agent layer canbe transported, stored, and used as intended. A crosslinked releaseagent layer and also a crosslinked component, therefore, in particularare no longer soft or tacky, having instead been conditioned to a solidrelease agent film or solid component, respectively. Even on furtherexposure to crosslinking conditions as described later on below, thefilm or component no longer exhibits any substantial change in itsproperties such as hardness or adhesion to the substrate.

As is known, release agent composition, and also the compositions (Z1,Z2, etc.) used in producing the component, may in principle be curedphysically and/or chemically, depending on the components included, suchas binders and crosslinking agents. The compositions are in particularcured chemically. Chemical curing comprehends thermochemical curing andactinic-chemical curing. The release agent and also the compositions(Z1, Z2, etc.), insofar as they are thermochemically curable, may beself-crosslinking and/or externally crosslinking. The term“self-crosslinking and/or externally crosslinking” in the context of thepresent invention means that the polymers included as binders andpossibly crosslinking agents are able to crosslink with one anotheraccordingly. The mechanisms involved and also the binders andcrosslinking agents (film-forming components) that can be used aredescribed later on below.

In the context of the present invention, “thermochemically curable” and,respectively, the term “thermochemical curing” refer to the crosslinkingof the composition (formation of a cured composition) that is initiatedby chemical reaction of reactive functional groups, with the possibilityof energetic activation of this chemical reaction by means of thermalenergy. Here, different functional groups, which are complementary toone another, may react with one another (complementary functionalgroups), and/or the formation of the cured composition is based on thereaction of autoreactive groups, these being functional groups whichreact with groups of their own kind. Examples of suitable complementaryreactive functional groups and autoreactive functional groups are knownfrom German patent application DE 199 30 665 A1, page 7, line 28 to page9, line 24, for example.

This crosslinking may be self-crosslinking and/or external crosslinking.Where, for example, the complementary reactive functional groups arealready present in an organic polymer used as binder, as for example ina polyester, a polyurethane or a poly(meth)acrylate, the crosslinkinginvolved is self-crosslinking. External crosslinking is involved, forexample, if a (first) organic polymer or a first compound containingparticular functional groups, hydroxyl groups for example, reacts with aconventional crosslinking agent, as for example with a polyisocyanateand/or with a melamine resin. The crosslinking agent therefore containsreactive functional groups which are complementary to the reactivefunctional groups present in the (first) organic polymer used as binder.

In the case of external crosslinking in particular, the systemscontemplated are the conventional multicomponent systems, especiallytwo-component systems. In these systems, the components to becrosslinked, as for example the organic polymers as binders and thecrosslinking agents, are present separately from one another in at leasttwo components, which are not combined until shortly before theapplication. This form is selected when the components to be crosslinkedreact with one another effectively even at ambient temperatures orslightly elevated temperatures of 40 to 90° C., for example. Acombination which may be stated by way of example is that ofhydroxy-functional polyesters and/or polyurethanes and/orpoly(meth)acrylates with free polyisocyanates as crosslinking agents.

It is also possible for an organic polymer as binder to have not onlyself-crosslinking but also externally crosslinking functional groups andto then be combined with crosslinking agents.

In the context of the present invention, “actinic-chemically curable” orthe term “actinic-chemical curing” refers to the fact that curing ispossible with application of actinic radiation, this beingelectromagnetic radiation such as near infrared (NIR) and UV radiation,especially UV radiation, and also particulate radiation such as electronbeams. Curing by UV radiation is customarily initiated by radical orcationic photoinitiators. Typical actinically curable functional groupsare carbon-carbon double bonds, in which case radical photoinitiatorsare generally employed. Actinic curing, then, is likewise based onchemical crosslinking.

In the curing of a composition labeled as being chemically curable,there will of course always be some physical curing, referring to theinterlooping of polymer chains. The physical curing may even account forthe major proportion. Nevertheless, a composition of this kind, if itcomprises at least proportionally film-forming components that arechemically curable, is referred to as being chemically curable.

It follows from the above that, according to the nature of the coatingcomposition and the components it comprises, curing is brought about bydifferent mechanisms, which of course also necessitate different curingconditions—in particular, different curing temperatures and curingtimes.

In principle and in the context of the present invention it is the casethat the curing of thermochemically curable two-component orthree-component systems can be carried out at temperatures of, forexample, 40 to 90° C., such as, in particular, 40 to 90° C., for aduration of 5 to 80 min, preferably 4 to 6 min. Accordingly it is thecase that there is a pre-cure flashing phase at lower temperaturesand/or for shorter times. A pre-cure flashing phase may run, forexample, at 15 to 90° C. for a duration of, for example, 0.2 to 2 min,but in any case for shorter times and/or at lower temperatures than thesubsequent curing.

All of the temperatures elucidated in the context of the presentinvention should be understood as the temperature of the molding tool inwhich the compositions are situated. It does not mean, therefore, thatthe compositions must themselves have the corresponding temperature.

The measurement methods to be employed in the context of the presentinvention for determining certain characteristic variables can be foundin the Examples section. Unless explicitly indicated otherwise, thesemeasurement methods are to be employed for determining the respectivecharacteristic variable. Where reference is made in the context of thepresent invention to an official standard without any indication of theofficial period of validity, the reference is implicitly to that versionof the standard that is valid on the filing date, or, in the absence ofany valid version at that point in time, to the last valid version.

Process of the Invention:

Within the process of the invention, a coated component is produced byinjection molding. This coated component in accordance with theinvention is preferably a sole, more particularly footwear sole, made ofplastic.

Process Step (A):

In step (A) of the process of the invention, a release agent compositionis applied to at least one inside of a molding part of a closablemolding tool. It is preferred in accordance with the invention if therelease agent composition is applied to all insides of all molding partsof the closable molding tool. This ensures that the compositions (Z1,Z2, etc.) and materials M1 used for producing the coated component donot remain attached to the insides of the molding parts during removal,and that damage-free removal of the coated component is ensured. Throughthe damage-free removal of the coated component, moreover, there is noneed for the molding tool to be cleaned after every production cycle.

It is preferred in accordance with the invention if the release agentcomposition is applied in process step (A) manually or using applicationrobots. The release agent composition used in the process of theinvention is in this case applied exactly like release agentcompositions known from the prior art. The degree of automation of theprocess of the invention can be enhanced by using application robots.The robots are programmed for the geometry of the sole molds and applythe release agent pneumatically and autonomously to the insides of themolding parts of the molding tool. The use of robots leads to anadditional boost in operational stability, since application is moreuniform. Moreover, the rate of application can be boosted by appropriateprogramming.

Where the release agent composition is applied by means of applicationrobots, it is preferred in accordance with the invention if, during theapplication of the release agent composition with deployment ofapplication robots, nozzles are used that have a diameter of 0.05 to 1.5mm, preferably of 0.08 to 1 mm, more particularly of 0.1 to 0.8 mm. Theuse of nozzles having the afore-described diameters ensures that theinsides of the molding parts of the molding tool are wetted completelywith a sufficient amount of release agent composition, while at the sametime preventing the application of too large a quantity of release agentcomposition.

The molding tool used in process step (A) may be at room temperature ormay have already been heated to a certain temperature. This temperature,however, must not be so high that the applied release agent compositionalready undergoes crosslinking, since in that case the composition nolonger adheres sufficiently to the composition Z1, Z2, etc. that is usedfor producing the component. Preferably in accordance with theinvention, therefore, the molding tool in process step (A) has atemperature of 20 to 100° C., more preferably 30 to 90° C., verypreferably 40 to 80° C., more particularly 50 to 70° C.

Release Agent Composition:

The composition of the invention preferably possesses a solids contentof 30 to 60 wt %, more preferably of 35 to 55 wt %, very preferably of40 to 50 wt %, more particularly of 42 to 48 wt %, based on the totalweight of the composition. The solids content was determined accordingto ASTM D2369 (2015) at 110° C. for 60 min on a 2 gram sample of thecomposition.

It is preferred in accordance with the invention, furthermore, if thecomposition has a viscosity of 10 to 60 s, more particularly of 20 to 30s (DIN4 flow cup), measured according to DIN EN ISO 2431 (March 2012).Establishing a low viscosity facilitates the application of thecomposition and therefore ensures sufficient wetting of the molding tooland also uniform coating of the component.

Release Agent Composition—Solvent L (a):

The release agent composition used in accordance with the invention maybe a solvent-based composition or an aqueous composition. In the case ofa solvent-based release agent composition, organic solvents are includedas a principal constituent. Organic solvents constitute volatileconstituents of the release agent composition, and undergo complete orpartial vaporization on drying or flashing, respectively. The principalconstituent of aqueous release agent compositions is water.

Preferably in accordance with the invention the at least one solvent Lis selected from organic solvents, water, and mixtures thereof, and ispresent in a total amount of 40 to 70 wt %, more preferably 45 to 65 wt%, and very preferably 50 to 60 wt %, especially 52 to 58 wt %, based ineach case on the total weight of the composition.

Organic solvents preferred in the context of the present invention areaprotic. With particular preference they are polar aprotic organicsolvents. With very particular preference the organic solvents arechemically inert toward the remaining constituents of the composition.

Preferred organic solvents in the context of the present invention are,for example, ketones such as acetone, methyl ethyl ketone,cyclohexanone, methyl isobutyl ketone, methyl isoamyl ketone ordiisobutyl ketone; esters such as ethyl acetate, n-butyl acetate,ethylene glycol diacetate, butyrolactone, diethyl carbonate, propylenecarbonate, ethylene carbonate, 2-methoxypropyl acetate (MPA), and ethylethoxypropionate; amides such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylpyrrolidone, and N-ethylpyrrolidone;methylal, butylal, 1,3-dioxolane, glycerol formal; and, somewhat lesspreferably because they are nonpolar, hydrocarbons such as benzene,toluene, n-hexane, cyclohexane, and solvent naphtha. Especiallypreferred solvents belong to the class of the esters, among whichn-butyl acetate and 1-methoxypropyl acetate are very especiallypreferred.

Release Agent Composition—Compound of the General Formula (I) (b):

The release agent composition used in accordance with the inventionfurther comprises a compound which may be rendered by the followingformula (I):

R¹—(C═O)_(r)—O-(AO)_(s)—R²   (I)

in which R¹ is a saturated or unsaturated, aliphatic hydrocarbon radicalhaving 6 to 30 carbon atoms, preferably 8 to 26, more preferably 10 to24, and very preferably 12 to 24 carbon atoms,

R² is H, a PO(OH)₂ radical, or the optionally partially phosphatedradical of a monosaccharide or disaccharide, or the optionally partiallyphosphated radical of an alditol, more particularly of sorbitol,

AO stands for one or more alkylene oxide radicals selected from thegroup consisting of ethylene oxide, propylene oxide and butylene oxide,

r is 0 or 1, and

s is 0 to 30, preferably 1 to 25 or 2 to 25, more preferably 4 to 22 or6 to 20, and very preferably 8 to 18.

The radical R¹ is preferably an acyclic radical.

The radicals AO may be identical or different and within the s radicalsmay have a random, blockwise or gradientlike arrangement. Where two ormore different kinds of AO are included, it is preferred if the fractionof ethylene oxide is more than 50 mol %, more preferably at least 70 mol%, and very preferably at least 90 mol %, based on the total molaramount of the radicals AO. In the aforementioned cases the radicalsdifferent from ethylene oxide are preferably propylene oxide radicals.

Where r=0 and s>0, the species of the formula (I) are alkoxylated fattyalcohols, preferably ethoxylated fatty alcohols, which optionally arephosphated (R²═PO(OH)₂) or etherified with a monosaccharide ordisaccharide or with the radical of an alditol. Where r=1 and s>0, thespecies of the formula (I) are alkoxylated fatty acids, preferablyethoxylated fatty acids, which optionally are phosphated (R²═PO(OH)₂) oretherified with a monosaccharide or disaccharide or with the radical ofan alditol.

Where s=0 and R² is the radical of a monosaccharide or disaccharide orthe radical of an alditol, then the species of formula (I) are fattyalcohol ethers of a monosaccharide or disaccharide or of an alditol(r=0) or are fatty acid esters of a monosaccharide or disaccharide or ofan alditol (r=1).

With particular preference, for some or all the species of the formula(I), s is 2 to 25, better still 6 to 20, and ideally 8 to 18, and/or,for some or all the species of the formula (I), s is 0 and R² is anoptionally partially phosphated radical of a monosaccharide ordisaccharide or is an optionally partially phosphated radical of analditol. With particular preference R¹ in this case is a saturated orunsaturated, aliphatic hydrocarbon radical having 10 to 24 carbon atoms.

In particular it is also possible to use mixtures of the species of theformula (I) in which s is 0 for at least one species while for at leastone further species s is >0, preferably 1 to 25 or 2 to 25, morepreferably 4 to 22 or 6 to 20, and very preferably 8 to 18.

With particular preference, in the general formula (I), R¹ is asaturated or unsaturated aliphatic hydrocarbon radical having 10 to 24carbon atoms, R² is H, a PO(OH)₂ radical, or the optionally partiallyphosphated radical of a monosaccharide or disaccharide, or theoptionally partially phosphated radical of an alditol, more particularlyof sorbitol, AO stands for one or more alkylene oxide radicals selectedfrom the group consisting of ethylene oxide and propylene oxide, r is 0or 1, and s is 0 or 1 to 25.

With further particular preference, in the general formula (I), R¹ is asaturated or unsaturated aliphatic hydrocarbon radical having 10 to 24carbon atoms, R² is H, a PO(OH)₂ radical, or the optionally partiallyphosphated radical of a monosaccharide or the optionally partiallyphosphated radical of an alditol, more particularly of sorbitol, AOstands for one or more alkylene oxide radicals selected from the groupconsisting of ethylene oxide and propylene oxide and the ethylene oxidefraction in the total molar amount of the radicals AO is at least 70 mol%, r=0 or 1, and s=0 or s=6 to 20.

Especially preferred are mixtures which comprise the aforesaidalkoxylated fatty alcohols with s>0 and/or the aforesaid alkoxylatedfatty acids with s>0 and at least one further species selected from thegroup encompassing

optionally phosphated or etherified fatty alcohols where r=s=0 and R²═H,PO(OH)₂, a monosaccharide radical, disaccharide radical or alditolradical, and

optionally phosphated or esterified fatty acids where r=1, s=0, andR²═H, PO(OH)₂, monosaccharide radical, disaccharide radical or alditolradical.

The total weight of the compound of the general formula (I) ispreferably 0.1 to 10 wt %, more preferably 0.5 to 5 wt %, moreparticularly 1.5 to 4 wt % based in each case on the total weight of therelease agent composition. Where more than one compound of the formula(I) is used, the quantity figures indicated above are based on the totalamount of all compounds which fall within the formula (I). If thecompound of the formula (I) is limited to a particular compound (I-1),then the quantities indicated above are based not merely on theparticular compound (I-1) but instead on the total amount of compoundswhich fall within the formula (I). If, for example, the compound (I-1)is used in an amount of 5 wt %, then there may be at most 7 wt % offurther compounds falling within the formula (I) present in the releaseagent composition.

Release Agent Composition—Polyether-Modified Alkyl-Polysiloxane (c):

The release agent composition used in accordance with the invention mayfurther comprise at least one polyether-modified alkylpolysiloxane. Theuse of such siloxanes leads to reduced dirt pickup of the coatedcomponents produced in accordance with the invention.

Preferably the polyether-modified alkylpolysiloxane comprises at leastone structural unit (R⁷)₂(OR⁶)SiO_(1/2) and at least one structural unit(R⁷)₂SiO_(2/2), where R⁶ is an ethylene oxide, propylene oxide, andbutylene oxide group, more particularly a mixture of ethylene oxide andpropylene oxide and butylene oxide groups, and R⁷ is a C₁-C₁₀ alkylgroup, more particularly a methyl group.

It is preferred in this context if the polyether-modifiedalkylpolysiloxane has a molar ratio of siloxane to ethylene oxide topropylene oxide to butylene oxide groups of 6:21:15:1 to 67:22:16:1.

It is preferred in this context, furthermore, if the polyether-modifiedalkylpolysiloxane has a molar ratio of the structural unit(R⁷)₂(OR⁶)SiO_(1/2) to the structural unit (R⁷)₂SiO_(2/2) of 1:10 to1:15, more particularly of 1:10 to 1:13. R⁶ and R⁷ here have thedefinitions recited above.

The release agent composition may comprise 0 wt % or 0.1 to 6 wt %,preferably 0.5 to 4 wt %, more particularly 0.8 to 3 wt %, based in eachcase on the total weight of the release agent composition, ofpolyether-modified alkylpolysiloxanes, more particularly of the specificpolyether-modified alkylpolysiloxanes recited above. The absence of suchcompounds makes the composition less tacky. As a result, the effect ofdemolding of the coated component produced from the molding tool isimproved.

Release Agent Composition—Polysiloxane of Formula (II) (d):

The release agent composition used in accordance with the inventionfurther comprises at least one polysiloxane of general formula (II)

R³—Si(R⁴)₂—[O—Si(R⁴)(R⁵)]_(a)—[O—Si(R⁴)₂]_(b)—O—Si(R⁴)₂—R³   (II),

in which

R³ and R⁴, in each case independently of one another, are a methyl groupor a (HO—CH₂)₂—C(CH₂—CH₃)—CH₂—O—(CH₂)₃—. radical,

R⁵ is a methyl group,

a is 0 or 1 to 10, and

b is 3 to 30.

The (HO—CH₂)₂—C(CH₂—CH₃)—CH₂—O—(CH₂)₃—. radical here is bonded via the .symbol to the silicon atom.

Used with preference in accordance with the invention are polysiloxaneswhich have particular radicals R³ and R⁴. The use of such polysiloxaneshas proven advantageous in relation to the improved demoldability, butwithout adversely affecting the adhesion of the crosslinked compositionof the invention to the component. In one preferred embodiment of thepresent invention, therefore, in the general formula (II), the radicalR³ is a (HO—CH₂)₂—C(CH₂—CH₃)—CH₂—O—(CH₂)₃—. radical, the radical R⁴ is amethyl group, the radical R⁵ is a methyl group, a is 0, and b is 7 to14.

Advantageously in accordance with the invention, the release agentcomposition comprises the at least one polysiloxane of the formula (II),more particularly the specific polysiloxanes recited above, in aparticular total amount. It is therefore preferred in accordance withthe invention if the release agent composition comprises the at leastone polysiloxane of the general formula (II) in a total amount of 0.1 to5 wt %, preferably 0.5 to 4 wt %, more particularly 0.8 to 2.5 wt %,based in each case on the total weight of the release agent composition.If more than one polysiloxane of the formula (II) is used, then thequantity figures indicated above are based on the total amount of allthe polysiloxanes which fall within the formula (II). If thepolysiloxane of the formula (II) is limited to particular polysiloxanes(II-1), then the quantities indicated above are based not only on theparticular polysiloxanes (II-1), but instead on the total amount ofpolysiloxanes which fall within the formula (II). Where, for example,the particular polysiloxanes (II-1) are used in an amount of 2 wt %,there may be at most 3 wt % of further polysiloxanes which fall withinthe formula (II) present in the release agent composition.

Release Agent Composition—Binder B (e):

With preference in accordance with the invention, the release agentcomposition, as well as the constituents described above, comprises atleast one binder B. The use of this binder B leads to the development ofa flexible and stable coating on the component, but without adverselyaffecting the demoldability of the component.

Surprisingly it has emerged that the nature of the binder B isimmaterial to the demoldability achieved with the release agentcomposition. A further surprise was that the release agent composition,independently of the binder B, has no adverse effect on the resultingcoating, particularly on its surface quality and flexibility. Therelease agent composition may therefore include any desired binders B,without adversely affecting demoldability of the component produced orthe outstanding properties of the coating produced with the compositionon the component. Moreover, the resulting coatings can be adhesivelybonded and/or coated with basecoat and/or clearcoat materials, withoutcostly and inconvenient aftertreatment steps.

The at least one binder B is present preferably in a total amount(solids content) of 20 to 50 wt %, more preferably of 25 to 40 wt %,more particularly 25 to 35 wt %, based in each case on the total weightof the composition. If the binder is a dispersion or solution in asolvent, the above-recited total quantities are calculated using thesolids content of the binder in each case. The use of the at least onebinder B in the above-recited quantity ranges ensures the development ofa flexible and stable coating on the component, but without adverselyaffecting the demoldability of the component.

With preference in accordance with the invention the binder B isselected from the group consisting of (i) poly(meth)acrylates, moreparticularly hydroxy-functional and/or carboxylate-functional and/oramine-functional poly(meth)acrylates, (ii) polyurethanes, moreparticularly hydroxy-functional and/or carboxylate-functional and/oramine-functional polyurethanes, (iii) polyesters, more particularlypolyester polyols, (iv) polyethers, more particularly polyether polyols,(v) copolymers in the stated polymers, and (vi) mixtures thereof.

It is preferred in this context that the binder B is selected fromhydroxy-functional poly(meth)acrylates and/or polyester polyols, moreparticularly from a mixture of at least one hydroxy-functionalpoly(meth)acrylate and at least one polyester polyol. The use of thismixture leads to coatings which have a high flexibility and also highresistance toward environmental influences. Moreover, irrespective ofthe surface nature of the material used for producing the component, asmooth surface is achieved. Furthermore, the coating obtained canwithout costly and inconvenient aftertreatment be adhesively bondedand/or coated with basecoat and/or clearcoat materials.

The at least one hydroxy-functional poly(meth)acrylate preferablypossesses a hydroxyl number of 65 to 100 mg KOH/g, more preferably of 70to 95 mg KOH/g, more particularly of 75 to 90 mg KOH/g or of 80 to 85 mgKOH/g. The hydroxyl number in the context of the present invention maybe determined according to EN ISO 4629-2:2016 and is based in each caseon the solids content.

The hydroxy-functional poly(meth)acrylate preferably possesses an acidnumber of less than 25 mg KOH/g, more preferably an acid number of 1 to20 mg KOH/g, very preferably of 4 to 16 mg KOH/g, more particularly of 6to 14 mg KOH/g or of 8 to 12 mg KOH/g. The acid number for the purposesof the present invention may be determined according to DIN EN ISO2114:2002-06 (method A) and is based in each case on the solids content.

The number-average molecular weight M_(n) and the weight-averagemolecular weight M_(w) may be determined by means of gel permeationchromatography (GPC) using a polymethyl methacrylate standard (PMMAstandard) (DIN 55672-1:2016-03). The number-average molecular weightM_(n) of the hydroxy-functional poly(meth)acrylate is preferably in arange from 4000 to 10 000 g/mol, more preferably 5000 to 9000 g/mol,very preferably 5500 to 8000 g/mol, more particularly 6000 to 7500g/mol. The weight-average molecular weight M_(w) of thehydroxy-functional poly(meth)acrylate is preferably in a range from 8000to 30 000 g/mol, more preferably 10 000 to 25 000 g/mol, very preferably12 000 to 22 000 g/mol, more particularly 14 000 to 20 000 g/mol. Thepolydispersity P_(D) (=M_(w)/M_(n)) of the hydroxy-functionalpoly(meth)acrylate is preferably in the range from 2 to 3, moreparticularly from 2.2 to 2.8.

The hydroxy-functional poly(meth)acrylate preferably possesses ahydroxyl functionality of 5 to 15, more preferably of 6 to 14, moreparticularly of 8 to 12.

The hydroxy-functional poly(meth)acrylate may be obtained by means ofthe polymerization reactions that are commonplace and familiar to aperson of ordinary skill in the art, from ethylenically unsaturatedmonomers, preferably monoethylenically unsaturated monomers. Initiatorswhich may be used include peroxides, such as di-tert-butyl peroxide, forexample.

It is therefore preferred for the hydroxy-functional poly(meth)acrylateto be preparable by reaction of

(a1) at least one hydroxy-functional (meth)acrylic ester, moreparticularly (meth)acrylic ester of the formula HC═CR^(x)—COO—R^(y)—OH,in which R^(x) is H or CH₃ and R^(y) is an alkylene radical having 2 to6, preferably 2 to 4, more preferably 2 or 3 carbon atoms,

(a2) at least one carboxy-functional ethylenically unsaturated monomer,more particularly (meth)acrylic acid, and

(a3) at least one hydroxyl-free and carboxyl-free ester of (meth)acrylicacid and/or at least one hydroxyl-free and carboxyl-free vinyl monomer,more particularly styrene.

The hydroxy groups present in the hydroxy-functional poly(meth)acrylateare introduced via hydroxy-functional ethylenically unsaturated monomers(a1), preferably hydroxy-functional acrylic esters and/orhydroxy-functional methacrylic esters, when preparing thehydroxy-functional poly(meth)acrylate. Examples of hydroxy-functional(meth)acrylates are hydroxyethyl methacrylate, hydroxyethyl acrylate,hydroxypropyl methacrylate, and hydroxypropyl acrylate. Present withparticular preference are hydroxyethyl methacrylate and 2-hydroxypropylmethacrylate. The amount of hydroxy-functional (meth)acrylic esters (a1)used in preparing the hydroxy-functional poly(meth)acrylates iscalculated on the basis of the target range for the hydroxyl number, of50 to 120 mg KOH/g.

The hydroxy-functional poly(meth)acrylate preferably contains smallquantities of carboxyl groups. These groups are introduced into thepoly(meth)acrylate during the polymerization reaction, through the use,for example, of carboxy-functional monomers (a2), more preferably ofacrylic acid and/or methacrylic acid. These monomers (a2), especially(meth)acrylic acid, are present preferably in a total amount of 20 to 45wt %, more preferably of 25 to 40 wt %, more particularly of 30 to 35 wt%, based in each case on the total weight of all the monomers used inpreparing the hydroxy-functional poly(meth)acrylate.

Besides the hydroxy-functional (a1) and the carboxy-functionalethylenically unsaturated monomers (a1), use is also made when preparingthe hydroxy-functional poly(meth)acrylate of ethylenically unsaturatedmonomers (a3), more particularly monoethylenically unsaturated monomers(a3), these monomers being free both of hydroxyl and of carboxyl groups.Employed with particular preference as vinyl monomer (a3) is styrene.The vinyl monomer (a3), more particularly styrene, is present preferablyin a total amount of 30 to 60 wt %, more preferably of 35 to 55 wt %,more particularly of 40 to 50 wt %, based in each case on the totalweight of all the monomers used in preparing the hydroxy-functionalpoly(meth)acrylate.

The hydroxy-functional poly(meth)acrylate may be used in an organicsolvent, preferably an aprotic solvent. A typical solvent for thispurpose, for example, is n-butyl acetate, which may also be used whenpreparing the at least one hydroxy-functional poly(meth)acrylate. If thehydroxy-functional poly(meth)acrylate is used in a solvent, then thesolvent is of course reckoned not as part of the constituent, butinstead as part of the solvent L.

The hydroxy-functional poly(meth)acrylate is preferably used in aparticular total quantity. It is therefore advantageous in accordancewith the invention if the hydroxy-functional poly(meth)acrylate ispresent in a total quantity of 10 wt % to 97 wt %, preferably of 40 to70 wt %, more particularly of 40 to 50 wt %, based in each case on thetotal weight of the solids content of all the binders present in thecomposition.

The polyester polyol preferably possesses a hydroxyl number of 100 to200 mg KOH/g, more preferably of 110 to 180 mg KOH/g, very preferably of120 to 160 mg KOH/g, based in each case on the solids content.

The acid number of the polyester polyol is preferably 0 to 9 mg KOH/g,more particularly 0.2 to 2 mg KOH/g, based in each case on the solidscontent. The hydroxyl number and acid number of the polyester polyol maybe determined as above in conjunction with the hydroxy-functionalpoly(meth)acrylate.

The number-average molecular weight of the polyester polyol ispreferably in the range from 800 to 3000 g/mol, more preferably 1000 to2000 g/mol, more particularly from 1000 to 1600 g/mol. The determinationhere is made as in connection with the determination of the molecularweight of the hydroxy-functional poly(meth)acrylate.

The polyester polyol is preferably branched.

The polyester polyol preferably possesses a hydroxyl functionality of2.2 to 4, more preferably of 2.5 to 3.6, very preferably of 2.7 to 3.6.

The polyester polyol is preferably used in a particular total quantity.It is therefore advantageous in accordance with the invention if thepolyester polyol is present in a total quantity of 40 wt % to 97 wt %,preferably of 40 to 70 wt %, more particularly of 50 to 65 wt %, basedin each case on the total weight of the solids content of all thebinders present in the composition.

The binder B may alternatively be selected from aqueous, anionicallystabilized polyurethane dispersions, aqueous, cationically stabilizedpolyurethane dispersions, aqueous polyurethane-polyurea dispersions, andmixtures thereof. Suitable dispersions are described, for example, inthe laid-open specifications EP 2 066 712 A1, EP 1 153 054 A1, and EP 1153 052 A1.

Release Agent Composition—Crosslinking Agent V (f):

It may be preferable in accordance with the invention if the releaseagent composition comprises not only the aforesaid constituents and/orthe at least one binder B but also a crosslinking agent V. Withparticular preference, the release agent composition used in accordancewith the invention comprises a combination of the above-described binderB and the below-described crosslinking agent V.

The crosslinking agent V is preferably selected from the groupsconsisting of amino resins, polyisocyanates, blocked polyisocyanates,polycarbodiimides, UV light, heat, photoinitiators, and mixturesthereof.

Particular preference is given to using polyisocyanates and alsopolycarbodiimides as crosslinking agents V.

The use of polyisocyanates has been found appropriate especially when amixture of the above-described at least one hydroxy-functionalpoly(meth)acrylate and the at least one polyester polyol is present asbinder B in the composition of the invention.

In this context it is particularly preferred if the polyisocyanatepossesses an NCO group functionality of greater than 2.4 to 5,preferably 2.6 to 4, more preferably 2.8 to 3.6.

Employed with particular preference in the context of the presentinvention are polyisocyanates which comprise at least one isocyanuratering or at least one iminooxadiazinedione ring.

According to an alternative embodiment, two polyisocyanates differentfrom one another may be present as crosslinking agents V, with the firstpolyisocyanate comprising at least one isocyanurate ring and the secondpolyisocyanate comprising at least one iminooxadiazinedione ring.

The polyisocyanate preferably comprises oligomers, preferably trimers ortetramers, of diisocyanates. With particular preference it comprisesiminooxadiazinediones, isocyanurates, allophanates and/or biurets ofdiisocyanates. With particular preference the polyisocyanate comprisesaliphatic and/or cycloaliphatic, very preferably aliphatic,polyisocyanates. Serving as a diisocyanate basis for the aforementionedoligomers, more particularly the aforementioned trimers or tetramers, isvery preferably hexamethylene diisocyanate and/or isophoronediisocyanate, and especially preferably just hexamethylene diisocyanate.

The use of polycarbodiimides has been found appropriate especially whenaqueous, anionically stabilized polyurethane dispersions, aqueous,cationically stabilized polyurethane dispersions, aqueouspolyurethane-polyurea dispersions, and mixtures thereof are present asbinders B in the composition of the invention.

The polycarbodiimides are preferably in the form of an aqueousdispersion. Polycarbodiimides used with particular preference areobtainable by reaction of polyisocyanates with polycarbodiimides andsubsequent chain extension and/or termination by means of hydrophiliccompounds containing hydroxyl groups and/or amine groups. Suitabledispersions are described in the laid-open specifications EP1644428 A2and EP1981922 A2, for example.

Through the crosslinking agent V it is possible to influence, forexample, the hardness, flexibility, and elasticity of the resultingcured coating. Use of polyisocyanates containing iminooxadiazinedionestructures, in particular, leads to coatings of particular hardness,thereby preventing substrate structures propagating through to the curedcoating surface and causing unwanted waviness there. Suchpolyisocyanates are available for example from Covestro under the nameDesmodur N3900. Similar results may be achieved with polyisocyanatescontaining isocyanurate structures, as available for example under thename Desmodur N3800 from Covestro, in which case the coating is stillhard but is more flexible.

The composition preferably comprises the at least one crosslinking agentV in a particular total quantity. It is therefore preferred inaccordance with the invention if the at least one crosslinking agent Vis present in a total quantity of 10 wt % to 40 wt %, preferably of 10to 30 wt %, more particularly of 15 to 25 wt %, based in each case onthe total weight of the composition.

It is preferred, furthermore, if the composition comprises a particularmolar ratio of the functional groups of the crosslinking agent V to thegroups of binder B that are reactive toward the crosslinking agent V.This ensures that crosslinking of the composition of the invention issufficient. It is therefore advantageous if the molar ratio of thefunctional groups of the crosslinking agent V, especially of the NCOgroups or carbodiimide groups, to the sum of the groups of the at leastone binder B, especially hydroxyl groups or anionic groups, that arereactive toward the functional groups of the crosslinking agent V is0.4:1 to 1:1, preferably 0.65:1 to 0.85:1, more particularly 0.7:1 to0.8:1.

Depending on the particular binders B and crosslinking agents V presentin the composition of the invention, the composition of the invention isconfigured as a one-component system or is obtainable by mixing two(two-component system) or more (multicomponent system) components. Inthermochemically curable one-component systems, the components to becrosslinked, in other words binder and crosslinking agent, are presentalongside one another, in other words in one component. A condition forthis is that the components to be crosslinked react with one anothereffectively only at relatively high temperatures, of more than 100° C.,for example, so as to prevent premature at least proportionalthermochemical curing. Such a combination may be exemplified byhydroxy-functional polyesters and/or polyurethanes with melamine resinsand/or blocked polyisocyanates as crosslinking agents.

In thermochemically curable two-component or multicomponent systems, thecomponents to be crosslinked, in other words binders and thecrosslinking agents, are present separately from one another in at leasttwo components, which are not combined until shortly before theapplication. This form is selected when the components to be crosslinkedreact with one another effectively even at ambient temperatures orslightly elevated temperatures of, for example, 40 to 90° C. Such acombination may be exemplified by hydroxy-functional polyesters and/orpolyurethanes and/or poly(meth)acrylates with free polyisocyanates ascrosslinking agents. Mixing may take place manually, with theappropriate amount of component 1 or 2 being introduced into a separatevessel, admixed with the corresponding quantity of component 2 or 1, andthen mixed. Provision may also be made, however, for the mixing of thetwo components to take place automatically, this being preferred in thecontext of the present invention. In one preferred embodiment of thepresent invention, therefore, the two components are mixed in anautomatic mixing system.

It is particularly preferred in this context if the automatic mixingsystem comprises a mixing unit, more particularly a static mixer, andalso at least two devices for supplying the paint base component A andthe curing component B, more particularly gear pumps and/or pressurevalves. The static mixer may be a commercially available helical mixer,which is installed into the material supply line about 50 to 100 cmahead of the atomizer. Preferably 12 to 18 mixing elements (for eachelement 1 cm in length, diameter 6 to 8 mm) are used in order to obtainsufficient mixing of the two components. Depending on the mixing energy,the potlife (doubling of the viscosity; determined according to DIN53211) of the release agent composition when the above-described 12 to18 mixing elements are used is 10 to 20 minutes. In order to preventclogging of the material supply line, it is preferred if the mixing unitis programmed so that not only the helical mixer but also the downstreamhose line and the atomizer are flushed with the paint base component Aevery 7 to 17 minutes. Where the release agent composition is applied bymeans of robots, this flushing operation takes place when the robot headis in a pre-defined position of rest. Depending on the length of thehose line, about 50 to 200 ml are discarded into a catch vessel. Apreferred alternative to this procedure is the semicontinuous conveyingof mixed release agent composition. If release agent composition isforced out regularly (every 7 to 17 minutes, likewise into a catchvessel), it is possible to reduce the quantity of discard material to aminimum (about 10 to 50 ml). Furthermore, provision may be made for thehose line from the mixer to the atomizer, and also the atomizer, to beflushed. This flushing operation is preferred in particular afterprolonged downtime of the system or at the end of a shift, in order thusto ensure a long lifetime of the equipment and continuous quality of therelease agent composition.

Also possible in principle is the utilization of a three-componentmixing system. This may simplify the stable storage of systems whichhave already been catalyzed, without giving rise to greater cost andcomplexity in terms of process engineering.

Both in the case of manual mixing and in the case of the supply of thecomponents for automatic mixing, the two components preferably eachpossess temperatures of to 70° C., more preferably 15 to 40° C., moreparticularly 20 to 30° C.

Where the composition of the invention is obtainable by mixing two ormore components, the weight ratio of the binder-containing component tothe crosslinker-containing component is preferably 100:10 to 100:100,more preferably from 100:20 to 100:80, more particularly from 100:50 to100:70. The use of the above-described mixing ratios ensures sufficientcrosslinking of the release agent composition and in that way providesan assurance of ready demoldability and also high adhesion to thesurface of the component produced.

Release Agent Composition—Crosslinking Catalyst VK (g):

Furthermore, it may be advantageous in accordance with the invention ifthe release agent composition comprises at least one crosslinkingcatalyst VK. The crosslinking catalyst VK is present especially when thecomposition comprises at least one crosslinking agent V, moreparticularly polyisocyanates.

The crosslinking catalyst VK serves primarily to catalyze the reactionbetween the functional groups of the crosslinking agent V and thereactive groups of the at least one binder B.

The crosslinking catalyst is preferably selected from the group of thebismuth carboxylates.

It is preferred in this context if specific bismuth carboxylates arepresent. The bismuth carboxylates therefore preferably possess thegeneral formula (III)

Bi[OOC(C_(n)H_(2n+1))]₃   (III)

where n=5 to 15, preferably n=7 to 13, more particularly n=9 to 11.

The carboxylate radicals are preferably branched, and very preferablythey have a tertiary or quaternary, preferably quaternary, carbon atomin the alpha-position to the carbon atom of the carboxylate group. Amongthe bismuth carboxylates, bismuth trineodecanoate in particular hasemerged as being especially suitable.

The bismuth carboxylates are preferably used in stabilized form incombination with the parent carboxylic acid of the carboxylate,HOOC(C_(n)H_(2n+1)), in which n possesses the definition indicatedabove. The free carboxylic acid here should formally not be regarded,for the purposes of this invention, as a constituent of the crosslinkingcatalyst VK, even if it may have not only the stabilizer effect butalso, optionally, may serve as a catalysis promoter; instead, it isincluded among the further additives as described below.

The composition preferably comprises the at least one crosslinkingcatalyst VK in a particular total quantity. It is therefore preferred inaccordance with the invention if the at least one crosslinking catalystVK is present in a total amount of 0.01 wt % to 3.5 wt %, preferably of0.1 to 2 wt %, more particularly of 0.4 to 1.5 wt %, based in each caseon the total weight of the composition.

Release Agent Composition—Color Base BF (h):

The release agent composition may further comprise at least one colorbase BF. A color base BF here means a colorant with a precisely definedhue. The at least one color base BF is present especially when a coloredcoating is to be obtained on the component. By using the at least onecolor base BF it is possible to achieve high accuracy of hue. Moreover,a high diversity of hue is possible, since different color bases BFhaving different hues can be mixed with one another in order to achievethe desired hue.

The at least one color base BF is present preferably in a particulartotal quantity in the release agent composition. It is thereforeadvantageous in accordance with the invention if the release agentcomposition comprises the at least one color base BF in a total quantityof 5 to 40 wt %, more particularly of 10 to 20 wt %, based on the totalweight of the composition. The use of the at least one color base BF inthe total quantities recited above ensures a high intensity of hue.

With particular preference the at least one color base BF comprises atleast one effect pigment and/or at least one coloring pigment.

Effect pigments are pigments which are able to produce a decorativeeffect in coatings and additionally, but not exclusively, to produce acoloring effect. The effect pigments are notable in particular for aplateletlike construction. Preferred effect pigments are, for example,platelet-shaped metallic effect pigments such as platelet-shapedaluminum pigments, gold bronzes, oxidized bronzes and/or ironoxide-aluminum pigments, pearlescent pigments and/or metal oxide-micapigments, and/or other effect pigments such as platelet-shaped graphite,platelet-shaped iron oxide, multilayer effect pigments composed of PVDfilms, and/or liquid crystal polymer pigments. Particularly preferredare platelet-shaped metallic effect pigments, more particularlyplatelet-shaped aluminum pigments and/or coated metal oxide-micapigments and/or borosilicates coated with metal oxides.

Examples of inorganic coloring pigments are white pigments such astitanium dioxide; black pigments such as carbon black, iron manganeseblack or spinel black; chromatic pigments such as ultramarine green,ultramarine blue or manganese blue, ultramarine violet or manganeseviolet, red iron oxide, molybdate red or ultramarine red; brown ironoxide, mixed brown, phases of spinel and corundum; or yellow iron oxideor bismuth vanadate. Examples of suitable organic coloring pigments aremonoazo pigments, disazo pigments, anthraquinone pigments, benzimidazolepigments, quinacridone pigments, quinophthalone pigments,diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments,isoindoline pigments, isoindolinone pigments, azomethine pigments,thioindigo pigments, metal complex pigments, perinone pigments, perylenepigments, phthalocyanine pigments or aniline black.

The at least one effect pigment and/or the at least one coloring pigmentare present preferably in a total amount of 0.5 to 70 wt %, based on thetotal weight of the color base BF.

Provision may also be made for the color base to comprise at least onebinder. This binder serves for stable dispersing of the pigment and inthat way ensures high intensity of hue and high homogeneity of hue onthe part of the color base BF.

Binders used in the color base BF are preferably polyurethane polymers,more particularly anionically stabilized polyurethane polymers. Byanionically stabilized polyurethane polymers are meant polyurethanepolymers which comprise at least one group that can be converted byneutralizing agents into an anionic group (i.e., a potentially anionicgroup). Examples of the potentially anionic groups which can beconverted into anionic groups by neutralizing agents include carboxylic,sulfonic and/or phosphonic acid groups, more particularly carboxylicacid groups.

The polyurethane polymers are obtainable by reaction of a prepolymercontaining isocyanate groups with compounds that are reactive towardisocyanate groups. The components are reacted preferably in thecustomary and known organic solvents. The amount of organic solvents mayvary within wide limits here, and ought to be sufficient for theformation of a prepolymer solution of suitable viscosity. In general upto 70 wt %, preferably 5 to 50 wt %, and more preferably less than 20 wt% of solvents are used, based on the solids content. Hence the reactionmay for example be carried out, especially preferably, at a solventcontent of 10 to 15 wt %, based on the solids content.

Polyurethane polymers of this kind preferably have a number-averagemolecular weight (determination: gel permeation chromatography withpolystyrene as standard) of 1000 to 30 000 g/mol, more preferably of1500 to 20 000 g/mol, and also an acid number of 5 to 70 mg KOH/g, morepreferably of 10 to 30 mg KOH/g (based on the solids content), and arepreparable by reaction, preferably chain extension, of prepolymerscontaining isocyanate groups.

The prepolymer containing isocyanate groups may be prepared by reactionof polyols having a hydroxyl number of 10 to 1800, preferably 50 to 1200mg KOH/g (based on the solids content) with excess polyisocyanates attemperatures up to 150° C., preferably 50 to 130° C., in organicsolvents which are unable to react with isocyanates. The equivalentratio of NCO groups to OH groups is between 2.0:1.0 and >1.0:1.0,preferably between 1.4:1 and 1.1:1.

The polyols used for preparing the NCO prepolymer may be of low and/orhigh molecular mass. For preparing anionically stabilized polyurethanepolymers, the polyols contain at least one anionic group and/or groupamenable to formation of anions. Also possible is the accompanying useof low molecular weight polyols having a molecular weight of 60 to 400daltons, for preparing the prepolymers containing isocyanate groups.

In order to obtain an NCO prepolymer having high flexibility, thefraction of a predominantly linear polyol that is added, with apreferred OH number of 30 to 150 mg KOH/g (based on the solids content),ought to be high. Up to 97 wt % of the total polyol may consist ofsaturated and unsaturated polyesters having a number-average molecularweight M_(n) of 400 to 5000 daltons. Polyester diols are prepared byesterification of organic dicarboxylic acids or their anhydrides withorganic diols, or derive from a hydroxycarboxylic acid or a lactone.Particular preference is given to using a linear polyester which isobtainable by reaction of aliphatic and aromatic dicarboxylic acids withaliphatic diols.

Besides the polyester, the NCO prepolymer is prepared using furtherpolyols, with at least one polyol having a carboxyl, sulfonic acidand/or phosphonic acid groups. Preferred for use are alkanoic acidshaving two hydroxyl groups on the carbon atom in alpha-position. Thesepolyols have at least one, generally 1 to 3 carboxyl groups in themolecule. They have two to about 25, preferably 3 to 10, carbon atoms.The carboxyl-containing polyol may account for 3 to 100 wt %, preferably5 to 50 wt %, of the overall polyol constituent in the NCO prepolymer.

The amount of ionizable carboxyl groups available through the carboxylgroup neutralization in salt form is at least 0.4 wt %, preferably atleast 0.7 wt %, based on the solids of the NCO prepolymer. The upperlimit is about 12 wt %. The amount of dihydroxyalkanoic acids in thenonneutralized prepolymer gives an acid number of mg KOH/g to 40 mgKOH/g (based on the solids content).

Further polyols, having no carboxyl, sulfonic acid and/or phosphonicacid groups, are preferably selected from C₃-C₈ alkanediols, especiallyfrom 1,6-hexanediol. These diols are used customarily in an amount of0.5 to 15 wt %, preferably 1 to 7 wt %, based in each case on the totalweight of the synthesis components used in preparing the anionicallystabilized polyurethane polymers.

Typical polyfunctional isocyanates used for preparing the anionicpolyurethane polymers are aliphatic, cycloaliphatic and/or aromaticpolyisocyanates having at least two isocyanate groups per molecule. Theisomers or isomer mixtures of organic diisocyanates are preferred. Onaccount of their high stability with respect to ultraviolet light,(cyclo)aliphatic diisocyanates result in products with a low tendency toyellow. The polyisocyanate component used to form the prepolymer mayalso include a fraction of higher polyisocyanates, provided this doesnot cause any gelling. Suitable triisocyanates are products which formby trimerization or oligomerization of diisocyanates or by reaction ofdiisocyanates with polyfunctional compounds containing OH or NH groups.The average functionality may optionally be lowered by addition ofmonoisocyanates.

Examples of polyisocyanates which can be used include phenylenediisocyanate, tolylene diisocyanate, xylylene diisocyanate, bisphenylenediisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate,isophorone diisocyanate, cyclobutane diisocyanate, cyclopentylenediisocyanate, cyclohexylene diisocyanate, methylcyclo-hexylenediisocyanate, dicyclohexylmethane diisocyanate, ethylene diisocyanate,trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylenediisocyanate, hexamethylene diisocyanate, propylene diisocyanate,ethylethylene diisocyanate, and trimethylhexane diisocyanate.

To prepare high-solids anionic polyurethane polymer dispersions, use ismade in particular of diisocyanates of the general formula (IV)

where X is a divalent cyclic and optionally aromatic hydrocarbonradical, preferably an optionally halogen-, methyl- ormethoxy-substituted dicyclohexylmethyl, naphthylene, diphenylene or1,2-, 1,3- or 1,4-phenylene radical, more preferably adicyclohexylmethyl radical, and R₃ and R₄ are hydrogen or an alkylradical having 1 to 4 carbons, and preferably are hydrogen. Onediisocyanate of the formula (IV) which is used with particularpreference in the context of the present invention is4,4′-methylenedicyclohexyl diisocyanate (also referred to as H₁₂MDI).

The NCO prepolymer contains at least 0.5 wt % of isocyanate groups,preferably at least 1 wt % of NCO, based on the solids. The upper limitis 15 wt %, preferably 10 wt %, more preferably 5 wt % of NCO.

The isocyanate groups of the prepolymer containing isocyanate groups arereacted with a modifier or chain extender. The modifier is preferablyadded in a quantity such that there are chain extensions and henceincreases in molecular weight. Modifiers used are preferably organiccompounds which comprise hydroxyl groups and/or secondary and/or primaryamino groups, especially polyols and/or polyamines having afunctionality of two, three and/or more. Examples of polyamines whichcan be used are ethylenediamine, trimethylenediamine,tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, ordiethylenetriamine. Examples of polyols which can be used aretrimethylolpropane, 1,3,4-butanetriol, glycerol, erythritol,mesoerythritol, arabitol, adonitol, etc. Preference is given to usingtrimethylolpropane. The equivalent ratio of NCO prepolymer to modifieris preferably between 2.0:1.0 and 1.0:2.0, more particularly between1.1:1 and 1:1.1.

In the context of the present invention, the anionically stabilizedpolyurethane polymer is obtainable with particular preference byreaction of an NCO prepolymer with a modifier in the form of a polyol,more particularly trimethylolpropane, the NCO prepolymer beingobtainable by reaction of

-   -   (i) 55 to 70 wt %, based on the total weight of the        compounds (i) to (iv), of at least one polyester polyol having        an OH number of 40 to 100 mg KOH/g, based on the solids content,        and a number-average molecular weight M_(n) of 1000 to 3000 Da,        the polyester polyol preferably containing no olefinic double        bonds,    -   (ii) 3 to 7 wt %, based on the total weight of the compounds (i)        to (iv), of at least one alkanoic acid having 3 to 8 carbon        atoms and also two hydroxyl groups on the carbon atom in        alpha-position, more particularly dimethylolpropionic acid,    -   (iii) 0.5 to 3 wt %, based on the total weight of the        compounds (i) to (iv), of at least one C₃-C₈ alkanediol, more        particularly 1,6-hexanediol, and    -   (iv) 25 to 30 wt %, based on the total weight of the        compounds (i) to (iv), of at least one diisocyanate of the        formula (IV) where X=dicyclohexylmethyl radical and        R₃═R₄=hydrogen.

The equivalent ratio of NCO prepolymer to modifier is preferably between2.0:1.0 and 1.0:2.0, more particularly between 1.1:1 and 1:1.1.

The anionically stabilized polyurethane polymer is neutralized with abase, preferably with an organic base, more particularly withN,N′-dimethylethanolamine, the base being added in a quantity such as toachieve a degree of neutralization of 50% to 100%, preferably of 60% to80%.

The at least one binder, more particularly the aforesaid anionicallystabilized polyurethane polymer, is present preferably in a quantity of10 to 80 wt %, based on the total weight of the color base BF.

The color base BF may also comprise at least one solvent. Solvents whichcan be used are those already stated above in connection with thesolvent L (component (a) of the composition of the invention). Employedwith particular preference is butyl glycol and/or methyl ethyl ketone.

In one particularly preferred embodiment of the color base BF,therefore, the color base BF, based on its total weight, comprises

(a1) 0.5 to 70 wt % of at least one effect pigment and/or at least onecoloring pigment,

(a2) 10 to 80 wt % of at least one binder selected from the group ofpolyurethane polymers, amino resin polymers, polyacrylate polymers,polyester polymers, and mixtures thereof, more particularly anabove-recited anionically stabilized polyurethane polymer, and

(a3) at least one organic solvent.

Release Agent Composition—Further Constituents (i)

Besides the above-recited constituents, the release agent compositionused in accordance with the invention may comprise further constituents.Examples of further constituents are additives.

The at least one additive is preferably selected from the groupconsisting of wetting agents and/or dispersants, rheological assistants,flow control agents, UV absorbers, and mixtures thereof.

The at least one additive is present preferably in a total quantity of 0wt % to 10 wt %, based on the total weight of the composition.

Process Step (B):

In process step B of the process of the invention, the release agentcomposition applied in step (A) is flashed. As already observed above,however, there is no crosslinking or curing of this composition in thisstep. In accordance with the invention, the flashing of the releaseagent composition in process step (B) takes place preferably for aperiod of 20 seconds to 120 minutes, more preferably of 20 seconds to 2minutes, more particularly of 25 seconds to 45 seconds. The extremelyshort flashing time of the release agent composition saves time in theregion of the flashing zone. One particularly preferred embodimentrequires flashing times of only 25 to 45 seconds, after which thefurther process steps can be carried out. As a result, an increase inproduction is possible.

The release agent composition is applied in step (A) preferably in aquantity such that a defined dry film thickness is obtained after theflashing in step (B). It is therefore preferred if the dry filmthickness of the flashed release agent composition in process step (B)is 20 to 120 μm, more particularly 25 to 100 μm. This ensures that thecoating produced on the component affords effective protection of thecomponent against mechanical stressing and also exposure toenvironmental influences.

To accelerate the flashing of the release agent composition it isadvantageous if the molding tool is heated. In process step (B) therelease agent composition is flashed preferably at a temperature of to100° C., more preferably 30 to 90° C., very preferably from 40 to 80°C., more particularly 50 to 70° C. The aforesaid temperatures result inrapid evaporation of the solvents present in the release agentcomposition, and also in formation of a film on the surface of theinsides of the molding parts of the molding tool. At these temperatures,however, there is not sufficient crosslinking or curing of the releaseagent composition. In this way it is ensured that there is nodeterioration in the adhesion between the release agent layer and thecompositions (Z1, Z2) and materials (M1) used in the further steps. Thisis because the high adhesion of the coating generated by the releaseagent on the surface of the component is achieved through simultaneouscrosslinking of the release agent and of the composition that forms thecomponent.

Process Step (C):

This process step is optional and therefore need not necessarily becarried out. If this step is carried out, then at least one material M1is inserted and the molding tool is heated in order to activate theinserted material. With particular preference, the material M1 insertedin process step (C) is an outsole, more particularly an outsole made ofthermoplastic polyurethane. Thermoplastic polyurethanes may be preparedby reaction of high molecular mass polyols, such as polyester polyolsand polyether polyols, having a number-average molecular weight of 500to 10 000 g/mol, with diisocyanates and also low molecular mass diols(M_(n) 50 to 499 g/mol). It is also possible, however, to use outsolesmade of other materials such as vulcanized or unvulcanized rubber andalso mixtures of rubber and plastics.

Especially when using thermoplastic materials Ml, it is advantageous ifthe molding tool is heated in process step (C) in order to render thematerial deformable and in that way to adapt it to the molding parts ofthe molding tool. It is therefore preferred if the molding tool isheated in process step (C) at 20 to 100° C., more preferably 30 to 90°C., very preferably 40 to 80° C., more particularly 50 to 70° C. Themolding tool can be heated by supplying heat or by irradiation, with IRradiation, for example. Preferably the molding tool is heated by meansof IR radiation.

Furthermore, provision may be made in accordance with the invention forthe molding tool to be closed after insertion of the at least onematerial M1, then heated, and subsequently opened again.

Process Step (D):

In process step (D), a composition Z1 is applied into the opened moldingtool, which optionally contains the material (M1) inserted beforehand.

Composition Z1 is a crosslinkable composition. Accordingly, either thecomposition must be self-crosslinking, or the composition must includecorresponding crosslinking agents. With particular preference, thecomposition Z1 applied in process step (D) is a polymer foam, moreparticularly a polyurethane foam material.

The polymer foams herein include, among others, elastomeric foams, moreparticularly flexible foams, but also thermoset foams, more particularlyrigid foams. The foams may be open-cell, closed-cell or mixed-cellfoams. The foams herein also include those known as integral foams.

Particularly preferred foams are polyurethane foam materials. These arecustomarily produced from one or more polyols and one or morepolyisocyanates. The blowing agent added to the polyol component to formthe foam is usually water, which reacts with part of the polyisocyanateto form carbon dioxide, the reaction therefore being accompanied byfoaming. Soft to elastic foams, especially flexible foams, are obtainedusing long-chain polyols. If short-chain polyols are used, highlycrosslinked structures are formed, leading generally to the formation ofrigid foams. The polyols used in producing the polyurethane foammaterials preferably comprise polyester polyols, polyether polyolsand/or polyester polyether polyols, and are accordingly selectedpreferably from the group of the aforesaid polyols.

Fibers as well may be admixed to the foam formulations. When suchformulations are foamed, the products are known as fiber-reinforcedfoams. Fibers are preferably used when producing rigid foams.

Application may take place by means of devices known in principle. Withparticular preference the composition Z1 is applied automatically inprocess step (D).

Provision may be made in accordance with the invention for thecomposition Z1 to be injected into the molding tool in a plurality ofstages. This is carried out especially when the sole mold of the moldingtool is divided into a plurality of fields. In that case the compositionZ1 in a first stage is injected into the first field and in a secondstage is injected into the second field. This technique is employed, forexample, when the first field represents an outsole and the second fieldrepresents a self-contained sole frame. In this case, the composition Z1is injected first into the mold compartment for the sole andsubsequently into the mold compartment of the self-contained sole frame.

Process Step (E):

In process step (E) of the process of the invention, the molding tool isclosed manually. Closing in this case may take place hydraulically orvia mechanical closures.

Process Step (F):

Crosslinking of the composition Z1 and of the release agent compositionintroduced beforehand takes place in process step (F) of the processaccording to the invention. The synchronous crosslinking of the twocompositions results in a high level of adhesion of the crosslinkedrelease agent coating to the cured composition Z1 and hence improves themechanical and optical properties of the resultant coated component.

To achieve crosslinking, process step (F) is preferably conducted atelevated temperatures. It is therefore advantageous if the crosslinkingin process step (F) takes place at temperatures of 45 to 75° C.,preferably 50 to 70° C., more particularly 52 to 65° C.

The crosslinking in process step (F) takes place preferably for a periodof 1 to 20 minutes, more preferably of 3 to 15 minutes, moreparticularly of 4 to 10 minutes. Such periods ensure sufficientcrosslinking of the release agent composition and also of thecomposition Z1 and therefore also permit easy demoldability of thecoated and cured composition Z1.

Process Step (G):

Provision may be made in accordance with the invention to apply andlikewise crosslink at least one further composition Z2. The compositionZ2 applied in process step (E) is preferably a polymer foam, moreparticularly a polyurethane foam material, which is preferably differentfrom the composition Z1. This process step may be repeated as often asdesired. Accordingly, it is also possible for further compositions Z3,Z4, etc., to be applied, preferably likewise being different from oneanother. The compositions may differ, for example, in density, in color,or in the material used. In this way, multilayer plastics soles can beproduced, the properties of the soles being adapted through the choiceof the compositions Z1, Z2, etc. If this step is carried out, the partsof the molding tool are preferably moved, before injection of thecomposition Z2, in such a way as to form in the molding tool a hollowcompartment into which the composition Z2 is injected. This may be done,for example, by moving the core plate or the molding part that closesthe molding tool at the top.

The curing or crosslinking of the compositions applied in step (G) takesplace as described for process step (F).

Process Step (H):

In process step (H) of the process of the invention, the molding tool isopened manually. Provision may be made in accordance with the inventionfor the position of at least one molding part of the molding tool to bealtered, in particular hydraulically, before the molding tool is opened.Furthermore, provision may be made requiring closure mechanisms for theclosing of the molding tool to be opened before the molding tool isopened.

Process Step (I):

In process step (I) of the process of the invention, the molded andcoated component is removed manually. The removal of the component maytake place with use of assistants.

Process Step (J):

Following removal of the coated component, provision may be made inaccordance with the invention for said component to be aftertreated. Theaftertreatment (J) preferably comprises trimming and/or polishing and/orlacquering of the coated component produced. The coated componentproduced may if desired be coated directly—without a grinding procedure,optionally after simple cleaning—with further coating materials such as,for example, with one or more basecoat materials and one or moreclearcoat materials, to form one or more basecoat films and one or moreclearcoat films, respectively. The component produced is preferably notcoated with a surfacer coat; instead, directly, a basecoat film or atopcoat film, more particularly a clearcoat film, is applied directly.In that case provision may be made for the basecoat film(s) and theclearcoat film(s) to be cured separately or jointly.

As basecoat and topcoat, more particularly clearcoat, materials it ispossible, in principle, to use all the basecoat and clearcoat materials,respectively, that are conventionally employed in lacquering. Suchbasecoat and clearcoat materials are available, for example, from BASFCoatings GmbH; clearcoat materials having been found particularlysuitable are, in particular, clearcoat materials of the EverGlossproduct line.

Further Process Steps:

Provision may be made in accordance with the invention for the processto comprise further process steps in addition to the mandatory processsteps (A), (B), and (D) to (I) and also the optional process steps (C)and (J). The process preferably includes a further process step inwhich, after the removal of the coated component in process step (I),the molding tool is cleaned, being more particularly cleaned manually.The molding tool may be cleaned by sandblasting or by use of organicsolvents. This cleaning step ensures that the surface of the moldingparts of the molding tool have no unwanted contaminants to lower theadhesion of the release agent composition to the surface of the moldingparts and hence to lower the release effect of the release agentcomposition.

In this context it is advantageous if the further process step iscarried out after 20 to 100, more particularly 20 to 50, repetitions ofthe process steps (A) to (I). Cleaning of the molding tool after anumber of 20 to 100 coated components produced permits an efficientprocess regime, since the molding tool does not have to be cleaned afterjust being used once. Furthermore, the quantity of cleaning wastes isreduced.

The process of the invention allows injection-molded, coated componentsto be produced, the components being able to be processed furtherwithout costly and inconvenient aftertreatment. Even without recoating,the coating obtained on the component by the release agent is highlyelastic or flexible and also UV-resistant and nonshiny, hence resultingnot only in damage-free demolding of the coated component but also ineffective protection of the coated component produced with respect toenvironmental influences such as UV radiation, dirt or the like, asearly as directly after the production of the coated component. Becausethe coating agent used in the process of the invention at the same timehas a release effect, this agent can be used both as a release agent andalso as a coating agent. Accordingly there is no need for the use of aseparate release agent, requiring costly and inconvenient removal beforeaftertreatment of the component. Furthermore, the coated componentsproduced have a regular surface even when produced using foams which, incombination with conventional release agents, lead to components havinga very irregular surface. Since only small residues of the release agentremain in the molding tool, the molding tools used do not have to becleaned before every further application of the release agent.

The invention is described in particular by the following embodiments:

According to a first embodiment, the present invention relates to amanual process for injection molding of coated components, moreparticularly soles of plastic, comprising the following steps in theorder indicated:

-   -   (A) application of a release agent composition to at least one        inside of at least one molding part of a closable molding tool,    -   (B) flashing of the release agent composition applied in step        (A),    -   (C) optional insertion of at least one material M1 and heating        of the molding tool,    -   (D) application of a composition Z1 into the opened molding        tool,    -   (E) manual closing of the molding tool,    -   (F) crosslinking of the release agent composition and also of        the composition Z1 applied in process step (D),    -   (G) optional application of at least one further composition Z2        and crosslinking of said composition(s),    -   (H) manual opening of the molding tool,    -   (I) manual removal of the molded coated component, and    -   (J) optional aftertreatment of the molded coated component,        where the release agent composition comprises:    -   (a) at least one solvent L,    -   (b) at least one compound of the general formula (I)

R¹—(C═O)_(r)—O-(AO)_(s)—R²   (I)

-   -   -   in which R¹ is a saturated or unsaturated, aliphatic            hydrocarbon radical having 6 to 30 carbon atoms,        -   R² is H, a PO(OH)2 radical, or the optionally partially            phosphated radical of a monosaccharide or disaccharide, or            the optionally partially phosphated radical of an alditol,        -   AO stands for one or more alkylene oxide radicals selected            from the group consisting of ethylene oxide, propylene oxide            and butylene oxide,        -   r is 0 or 1, and s is 0 to 30;

    -   (c) optionally at least one polyether-modified        alkylpolysiloxane,

    -   (d) at least one polysiloxane of the general formula (II)

R³—Si(R⁴)₂—[O—Si(R⁴)(R⁵)]_(a)—[O—Si(R⁴)₂]_(b)—O—Si(R⁴)₂—R³   (II),

-   -   -   in which        -   R³ and R⁴, in each case independently of one another, are a            methyl group or a (HO—CH₂)₂—C(CH₂—CH₃)—CH₂—O—(CH₂)₃—.            radical,        -   R⁵ is a methyl group,        -   a is 0 or 1 to 10, and        -   b is 3 to 30; and

    -   (e) optionally at least one binder B.

According to a second embodiment, the present invention relates to amanual process according to embodiment 1, wherein the release agentcomposition is applied in process step (A) manually or using applicationrobots.

According to a third embodiment, the present invention relates to amanual process according to embodiment 2, wherein, on application of therelease agent composition using application robots, nozzles are usedthat have a diameter of 0.05 to 1.5 mm, preferably of 0.08 to 1 mm, moreparticularly of 0.1 to 0.8 mm.

According to a fourth embodiment, the present invention relates to amanual process according to any of the preceding embodiments, whereinthe molding tool in process step (A) has a temperature of 20 to 100° C.,more preferably 30 to 90° C., very preferably 40 to 80° C., moreparticularly 50 to 70° C.

According to a fifth embodiment, the present invention relates to amanual process according to any of the preceding embodiments, whereinthe release agent composition is provided in an automatic mixing system.

According to a sixth embodiment, the present invention relates to amanual process according to embodiment 5, wherein the automatic mixingsystem comprises a mixing unit, more particularly a static mixer, andalso at least two devices for the supply of components, moreparticularly gear pumps and/or pressure valves.

According to a seventh embodiment, the present invention relates to amanual process according to any of the preceding embodiments, whereinthe release agent composition has a viscosity of 10 to 60 s, moreparticularly of 20 to 30 s (DIN4 flow cup), measured according to DIN ENISO 2431 (March 2012).

According to an eighth embodiment, the present invention relates to amanual process according to any of the preceding embodiments, whereinthe release agent composition has a solids content of 30 to 60 wt %,preferably of 35 to 55 wt %, more preferably of 40 to 50 wt %, moreparticularly of 42 to 48 wt %, measured according to ASTM D2369 (2015)(110° C., 60 min).

According to a ninth embodiment, the present invention relates to amanual process according to any of the preceding embodiments, whereinthe at least one solvent L is selected from organic solvents, water, andmixtures thereof and is present in a total quantity of 40 to 70 wt %,more preferably 45 to 65 wt %, and very preferably 50 to 60 wt %, moreparticularly 52 to 58 wt %, based in each case on the total weight ofthe composition.

According to a tenth embodiment, the present invention relates to amanual process according to any of the preceding embodiments, wherein,in the general formula (I), R¹ is a saturated or unsaturated aliphatichydrocarbon radical having 10 to 24 carbon atoms, R² is H, a PO(OH)₂radical, or the optionally partially phosphated radical of amonosaccharide or disaccharide, or the optionally partially phosphatedradical of an alditol, more particularly of sorbitol, AO stands for oneor more alkylene oxide radicals selected from the group consisting ofethylene oxide and propylene oxide, r is 0 or 1, and s is 0 or 1 to 25.

According to an eleventh embodiment, the present invention relates to amanual process according to any of the preceding embodiments, wherein,in the general formula (I), R¹ is a saturated or unsaturated, aliphatichydrocarbon radical having 10 to 24 carbon atoms, R² is H, a PO(OH)₂radical, or the optionally partially phosphated radical of amonosaccharide or the optionally partially phosphated radical of analditol, more particularly of sorbitol, AO stands for one or morealkylene oxide radicals selected from the group consisting of ethyleneoxide and propylene oxide, and the ethylene oxide fraction in theentirety of the radicals AO is at least 70 mol %, r is 0 or 1, and s is0 or s is 6 to 20.

According to a twelfth embodiment, the present invention relates to amanual process according to any of the preceding embodiments, whereinthe at least one compound of the general formula (I) is present in atotal quantity of 0.1 to 10 wt %, more preferably 0.5 to 5 wt %, moreparticularly 1.5 to 4 wt %, based in each case on the total weight ofthe release agent composition.

According to a thirteenth embodiment, the present invention relates to amanual process according to any of the preceding embodiments, whereinthe polyether-modified alkylpolysiloxane comprises at least onestructural unit (R⁷)₂(OR⁶)SiO_(1/2) and at least one structural unit(R⁷)₂SiO_(2/2), where R⁶ is an ethylene oxide, propylene oxide, andbutylene oxide group, more particularly a mixture of ethylene oxide andpropylene oxide and butylene oxide groups, and R⁷ is a C₁-C₁₀ alkylgroup, more particularly a methyl group.

According to a fourteenth embodiment, the present invention relates to amanual process according to embodiment 13, wherein thepolyether-modified alkyl-polysiloxane has a molar ratio of siloxane toethylene oxide groups to propylene oxide groups to butylene oxide groupsof 6:21:15:1 to 67:22:16:1.

According to a fifteenth embodiment, the present invention relates to amanual process according to either of embodiments 13 or 14, wherein thepolyether-modified alkylpolysiloxane has a molar ratio of the structuralunit (R⁷)₂(OR⁶)SiO_(1/2) to the structural unit (R⁷)₂SiO_(2/2) of 1:10to 1:15, more particularly of 1:10 to 1:13.

According to a sixteenth embodiment, the present invention relates to amanual process according to any of the preceding embodiments, whereinthe at least one polyether-modified alkylpolysiloxane is present in atotal amount of 0 wt % or of 0.1 to 6 wt %, preferably 0.5 to 4 wt %,more particularly 0.8 to 3 wt %, based in each case on the total weightof the release agent composition.

According to a seventeenth embodiment, the present invention relates toa manual process according to any of the preceding embodiments, wherein,in the general formula (II), the radical R³ is a(HO—CH₂)₂—C(CH₂—CH₃)—CH₂—O—(CH₂)₃—. radical, the radical R⁴ is a methylgroup, the radical R⁵ is a methyl group, a is 0, and b is 7 to 14.

According to an eighteenth embodiment, the present invention relates toa manual process according to any of the preceding embodiments, whereinsaid composition comprises the at least one polysiloxane of the generalformula (II) in a total amount of 0.1 to 5 wt %, preferably 0.5 to 4 wt%, more particularly 0.8 to 2.5 wt %, based in each case on the totalweight of the release agent composition.

According to a nineteenth embodiment, the present invention relates to amanual process according to any of the preceding embodiments, whereinthe at least one binder B is present in a total quantity (solidscontent) of 20 to 50 wt %, preferably of 25 to 40 wt %, moreparticularly of 25 to 35 wt %, based in each case on the total weight ofthe composition.

According to a twentieth embodiment, the present invention relates to amanual process according to any of the preceding embodiments, whereinthe binder B is selected from the group consisting of (i)poly(meth)acrylates, more particularly hydroxy-functional and/orcarboxylate-functional and/or amine-functional poly(meth)acrylates, (ii)polyurethanes, more particularly hydroxy-functional and/orcarboxylate-functional and/or amine-functional polyurethanes, (iii)polyesters, more particularly polyester polyols, (iv) polyethers, moreparticularly polyether polyols, (v) copolymers in the stated polymers,and (vi) mixtures thereof.

According to a twenty-first embodiment, the present invention relates toa manual process according to embodiment 20, wherein the binder B isselected from hydroxy-functional poly(meth)acrylates and/or polyesterpolyols, more particularly from a mixture of at least onehydroxy-functional poly(meth)acrylate and at least one polyester polyol.

According to a twenty-second embodiment, the present invention relatesto a manual process according to either of the preceding embodiments 20and 21, wherein the hydroxy-functional poly(meth)acrylate has a hydroxylnumber of 50 to 120 mg KOH/g, preferably of 70 to 95 mg KOH/g, moreparticularly of 75 to 90 mg KOH/g or of 80 to 85 mg KOH/g.

According to a twenty-third embodiment, the present invention relates toa manual process according to any of the preceding embodiments 20 to 22,wherein the hydroxy-functional poly(meth)acrylate has an acid number of1 to 20 mg KOH/g, more particularly 6 to 14 mg KOH/g or 8 to 12 mgKOH/g, and/or possesses a number-average molecular weight M_(n) of 4000to 10 000 g/mol, preferably 5000 to 9000 g/mol, more preferably 5500 to8000 g/mol, more particularly 6000 to 7500 g/mol.

According to a twenty-fourth embodiment, the present invention relatesto a manual process according to any of the preceding embodiments 20 to23, wherein the hydroxy-functional poly(meth)acrylate has a hydroxylfunctionality of 5 to 15, preferably of 6 to 14, more particularly of 8to 12.

According to a twenty-fifth embodiment, the present invention relates toa manual process according to any of the preceding embodiments 20 to 24,wherein the hydroxy-functional poly(meth)acrylate is preparable byreaction of

(a1) at least one hydroxy-functional (meth)acrylic ester, moreparticularly (meth)acrylic ester of the formula HC═CR^(x)—COO—R^(y)—OH,in which R^(x) is H or CH₃ and R^(y) is an alkylene radical having 2 to6, preferably 2 to 4, more preferably 2 or 3 carbon atoms,

(a2) at least one carboxy-functional ethylenically unsaturated monomer,more particularly (meth)acrylic acid, and

(a3) at least one hydroxyl-free and carboxyl-free ester of (meth)acrylicacid and/or at least one hydroxyl-free and carboxyl-free vinyl monomer,more particularly styrene.

According to a twenty-sixth embodiment, the present invention relates toa manual process according to embodiment 25, wherein thecarboxy-functional ethylenically unsaturated monomer (a2), moreparticularly (meth)acrylic acid, is present in a total quantity of 20 to45 wt %, preferably of 25 to 40 wt %, more particularly of 30 to 35 wt%, based in each case on the total weight of all the monomers used inpreparing the hydroxy-functional poly(meth)acrylate.

According to a twenty-seventh embodiment, the present invention relatesto a manual process according to either of the preceding embodiments 25or 26, wherein the vinyl monomer (a3), more particularly styrene, ispresent in a total quantity of 30 to 60 wt %, preferably of 35 to 55 wt%, more particularly of 40 to 50 wt %, based in each case on the totalweight of all the monomers used in preparing the hydroxy-functionalpoly(meth)acrylate.

According to a twenty-eighth embodiment, the present invention relatesto a manual process according to any of the preceding embodiments 20 to27, wherein the hydroxy-functional poly(meth)acrylate is present in atotal quantity of 10 wt % to 97 wt %, preferably of 40 to 70 wt %, moreparticularly of 40 to 50 wt %, based in each case on the total weight ofthe solids content of all binders present in the release agentcomposition.

According to a twenty-ninth embodiment, the present invention relates toa manual process according to any of the preceding embodiments 20 to 28,wherein the polyester polyol has a hydroxyl number of 100 to 200 mgKOH/g, preferably of 110 to 180 mg KOH/g, more particularly of 120 to160 mg KOH/g.

According to a thirtieth embodiment, the present invention relates to amanual process according to any of the preceding embodiments 20 to 29,wherein the polyester polyol has an acid number of 0 to 9 mg KOH/g, moreparticularly 0.2 to 2 mg KOH/g, and/or possesses a number-averagemolecular weight of 800 to 3000 g/mol, preferably 1000 to 2000 g/mol,more particularly of 1000 to 1600 g/mol.

According to a thirty-first embodiment, the present invention relates toa manual process according to any of the preceding embodiments 20 to 30,wherein the polyester polyol is branched.

According to a thirty-second embodiment, the present invention relatesto a manual process according to any of the preceding embodiments 20 to31, wherein the polyester polyol has a hydroxyl functionality of 2.2 to4, preferably of 2.5 to 3.6, more particularly of 2.7 to 3.6.

According to a thirty-third embodiment, the present invention relates toa manual process according to any of the preceding embodiments 20 to 32,wherein the polyester polyol is present in a total quantity of 40 wt %to 97 wt %, preferably of 40 to 70 wt %, more particularly of 50 to 65wt %, based in each case on the total weight of the solids content ofall binders present in the composition.

According to a thirty-fourth embodiment, the present invention relatesto a manual process according to any of the preceding embodiments,wherein the release agent composition additionally comprises at leastone crosslinking agent V.

According to a thirty-fifth embodiment, the present invention relates toa manual process according to embodiment 34, wherein the crosslinkingagent V is selected from the group consisting of amino resins,polyisocyanates, blocked polyisocyanates, polycarbodiimides, UV light,heat, photoinitiators, and mixtures thereof.

According to a thirty-sixth embodiment, the present invention relates toa manual process according to embodiment 35, wherein the polyisocyanatepossesses an NCO group functionality of greater than 2.4 to 5,preferably 2.6 to 4, more preferably 2.8 to 3.6.

According to a thirty-seventh embodiment, the present invention relatesto a manual process according to either of the preceding embodiments 35and 36, wherein the polyisocyanate comprises at least one isocyanuratering or at least one iminooxadiazinedione ring.

According to a thirty-eighth embodiment, the present invention relatesto a manual process according to either of the preceding embodiments 35and 36, wherein two polyisocyanates different from one another arepresent, the first polyisocyanate comprising at least one isocyanuratering and the second polyisocyanate comprising at least oneiminooxadiazinedione ring.

According to a thirty-ninth embodiment, the present invention relates toa manual process according to any of the preceding embodiments 34 to 38,wherein the at least one crosslinking agent V is present in a totalquantity of 10 wt % to 40 wt %, preferably of 10 to 30 wt %, moreparticularly of 15 to 25 wt %, based in each case on the total weight ofthe release agent composition.

According to a fortieth embodiment, the present invention relates to amanual process according to any of the preceding embodiments 20 to 39,wherein the molar ratio of the functional groups of the crosslinkingagent V, more particularly of the NCO groups or carbodiimide groups, tothe sum of the groups in the at least one binder B, more particularlyhydroxyl groups, that are reactive toward the functional groups of thecrosslinking agent V is 0.4:1 to 1:1, preferably 0.65:1 to 0.85:1, moreparticularly 0.7:1 to 0.8:1.

According to a forty-first embodiment, the present invention relates toa manual process according to any of the preceding embodiments, whereinthe release agent composition additionally comprises at least onecrosslinking catalyst VK.

According to a forty-second embodiment, the present invention relates toa manual process according to embodiment 41, wherein the crosslinkingcatalyst VK is selected from the group of the bismuth carboxylates.

According to a forty-third embodiment, the present invention relates toa manual process according to embodiment 42, wherein the crosslinkingcatalyst VK from the group of the bismuth carboxylates has the generalformula (III)

Bi[OOC(C_(n)H_(2n+1))]₃   (III)

where n=5 to 15, preferably n=7 to 13, more particularly n=9 to 11.

According to a forty-fourth embodiment, the present invention relates toa manual process according to any of the preceding embodiments 41 to 43,wherein the at least one crosslinking catalyst VK is present in a totalquantity of 0.01 wt % to 3.5 wt %, preferably of 0.1 to 2 wt %, moreparticularly of 0.4 to 1.5 wt %, based in each case on the total weightof the release agent composition.

According to a forty-fifth embodiment, the present invention relates toa composition according to any of the preceding embodiments, wherein therelease agent composition additionally comprises at least one color baseBF.

According to a forty-sixth embodiment, the present invention relates toa composition according to embodiment 45, wherein at least one colorbase BF is present in a total quantity of 5 to 40 wt %, moreparticularly of 10 to 20 wt %, based on the total weight of thecomposition.

According to a forty-seventh embodiment, the present invention relatesto a composition according to either of the embodiments 45 and 46,wherein the color base BF comprises at least one effect pigment and/orat least one coloring pigment, preferably in a total quantity of 0.5 to70 wt %, based on the total weight of the color base BF.

According to a forty-eighth embodiment, the present invention relates toa composition according to embodiment 46, wherein the at least oneeffect pigment (a1) is selected from the group of platelet-shapedmetallic effect pigments, pearlescent pigments, metal oxide-micapigments, platelet-shaped graphite, platelet-shaped iron oxide,multilayer effect pigments from PVD films, liquid crystal polymerpigments, and mixtures thereof, more particularly from platelet-shapedaluminum pigments and/or coated metal oxide-mica pigments and/or metaloxide-coated borosilicates.

According to a forty-ninth embodiment, the present invention relates toa composition according to either of the embodiments 47 and 48, whereinthe at least one coloring pigment (a1) is selected from the group ofwhite pigments, black pigments, chromatic pigments, monoazo pigments,disazo pigments, anthraquinone pigments, benzimidazole pigments,quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrolepigments, dioxazine pigments, indanthrone pigments, isoindolinepigments, isoindolinone pigments, azomethine pigments, thioindigopigments, metal complex pigments, perinone pigments, perylene pigments,phthalocyanine pigments, aniline black, and mixtures thereof.

According to a fiftieth embodiment, the present invention relates to acomposition according to any of the embodiments 45 to 49, wherein thecolor base BF comprises at least one binder selected from the group ofpolyurethane polymers, amino resin polymers, polyacrylate polymers,polyester polymers, and mixtures thereof, especially anionicallystabilized polyurethane polymers, preferably in a total quantity of 10to 80 wt %, based on the total weight of the color base BF.

According to a fifty-first embodiment, the present invention relates toa composition according to embodiment 50, wherein the anionicallystabilized polyurethane polymer is obtainable by reaction of an NCOprepolymer with a modifier in the form of a polyol, more particularlytrimethylolpropane, the NCO prepolymer being obtainable by reaction of

-   -   (i) 55 to 70 wt %, based on the total weight of the        compounds (i) to (iv), of at least one polyester polyol having        an OH number of 40 to 100 mg KOH/g, based on the solids content,        and a number-average molecular weight Mn of 1000 to 3000 Da, the        polyester polyol preferably containing no olefinic double bonds,    -   (ii) 3 to 7 wt %, based on the total weight of the compounds (i)        to (iv), of at least one alkanoic acid having 3 to 8 carbon        atoms and also two hydroxyl groups on the carbon atom in        alpha-position, more particularly dimethylolpropionic acid,    -   (iii) 0.5 to 3 wt %, based on the total weight of the        compounds (i) to (iv), of at least one C₃-C₈ alkanediol, more        particularly 1,6-hexanediol, and    -   (iv) 25 to 30 wt %, based on the total weight of the        compounds (i) to (iv), of at least one diisocyanate of the        formula (IV) where X=dicyclohexylmethyl radical and        R₃═R₄=hydrogen,        where the equivalent ratio of NCO prepolymer to modifier is        between 2.0:1.0 and 1.0:2.0, more particularly between 1.1:1 and        1:1.1.

According to a fifty-second embodiment, the present invention relates toa composition according to either of the embodiments 50 and 51, whereinthe anionically stabilized polyurethane polymer has a degree ofneutralization of 50% to 100%, preferably of 60% to 80%.

According to a fifty-third embodiment, the present invention relates toa manual process according to any of the preceding embodiments, whereinat least one additive selected from the group consisting of wettingagents and/or dispersants, rheological assistants, flow control agents,UV absorbers, and mixtures thereof is additionally present.

According to a fifty-fourth embodiment, the present invention relates toa manual process according to embodiment 53, wherein the at least oneadditive is present in a total quantity of 0 wt % to 10 wt %, based onthe total weight of the composition.

According to a fifty-fifth embodiment, the present invention relates toa manual process according to any of the preceding embodiments, whereinthe release agent composition is flashed in process step (B) for aperiod of 20 seconds to 120 minutes, preferably of 20 seconds to 2minutes, more particularly of 25 seconds to 45 seconds.

According to a fifty-sixth embodiment, the present invention relates toa manual process according to any of the preceding embodiments, whereinthe dry film thickness of the flashed release agent composition inprocess step (B) is 20 to 120 μm, more particularly 25 to 100 μm.

According to a fifty-seventh embodiment, the present invention relatesto a manual process according to any of the preceding embodiments,wherein the release agent composition is flashed in process step (B) ata temperature of 20 to 100° C., more preferably 30 to 90° C., verypreferably 40 to 80° C., more particularly 50 to 70° C.

According to a fifty-eighth embodiment, the present invention relates toa manual process according to any of the preceding embodiments, whereinthe material M1 inserted in process step (C) is an outsole, moreparticularly an outsole made of thermoplastic polyurethane.

According to a fifty-ninth embodiment, the present invention relates toa manual process according to any of the preceding embodiments, whereinthe molding tool is heated in process step (C) at 20 to 100° C., morepreferably 30 to 90° C., very preferably 40 to 80° C., more particularly50 to 70° C.

According to a sixtieth embodiment, the present invention relates to amanual process according to any of the preceding embodiments, whereinthe composition Z1 applied in process step (D) is a polymer foam, moreparticularly a polyurethane foam material.

According to a sixty-first embodiment, the present invention relates toa manual process according to any of the preceding embodiments, whereinthe composition Z1 is applied automatically in process step (D).

According to a sixty-second embodiment, the present invention relates toa manual process according to any of the preceding embodiments, whereinthe crosslinking in process step (F) takes place at temperatures of 45to 75° C., preferably 50 to 70° C., more particularly 52 to 65° C.

According to a sixty-third embodiment, the present invention relates toa manual process according to any of the preceding embodiments, whereinthe crosslinking in process step (F) takes place for a period of 1 to 20minutes, preferably after 3 to 15 minutes, more particularly after 4 to10 minutes.

According to a sixty-fourth embodiment, the present invention relates toa manual process according to any of the preceding embodiments, whereinthe composition Z2 applied in process step (G) is a polymer foam, moreparticularly a polyurethane foam material, which is preferably differentfrom the composition Z1.

According to a sixty-fifth embodiment, the present invention relates toa manual process according to any of the preceding embodiments, whereinthe after-treatment (J) comprises trimming and/or polishing and/orlacquering of the component produced and coated.

According to a sixty-sixth embodiment, the present invention relates toa manual process according to embodiment 65, wherein the aftertreatment(J) comprises lacquering, where to the coating of the component, withoutan intermediate grinding procedure, at least one basecoat film and/or atleast one clearcoat film is applied, and where the basecoat film(s) andclearcoat film(s) are cured separately or jointly.

According to a sixty-seventh embodiment, the present invention relatesto a manual process according to any of the preceding embodiments,wherein the process comprises a further process step in which themolding tool, after the removal of the coated component in process step(I), is cleaned, more particularly manually cleaned.

According to a sixty-eighth embodiment, the present invention relates toa manual process according to embodiment 67, wherein the further processstep is carried out after 20 to 100, more particularly 20 to 50,repetitions of process steps (A) to (I).

EXAMPLES

Description of Methods:

1. Solids Content (Solids, Nonvolatile Fraction)

The nonvolatile fraction is determined according to ASTM D2369 (date:2015). In this procedure, 2 g of sample are weighed out into an aluminumdish which has been dried beforehand, and the sample is dried in adrying cabinet at 110° C. for 60 minutes, cooled in a desiccator, andthen reweighed. The residue, relative to the total amount of sampleintroduced, corresponds to the nonvolatile fraction.

2. Determination of Demolding Energy

In this case an adhesive strip (TESA 4651; see Tesa datasheet) withdimensions of 2.5×4 cm is bonded to the upper side of a molding tool.Beforehand at one end the adhesive tape is folded over once to give aloop, through which a hole is drilled. The spring balance is suspendedin this hole. Using a scalpel, the coating film is cut through aroundthe adhesive tape, to give a defined area of 10 cm². The removaldirection is orthogonal to the molding tool.

3. Capacity for Further Processing

The respective release agent composition was applied to a molding toolsurface at 55° C. Directly after the end of application, a fingertip wasused to dab the liquid release agent composition in a 5-second cycle, asfar as possible uniformly/with constant pressure. The respective releaseagent composition had capacity for further processing as soon as it hadfully dried but could not be detached from the molding tool.

4. Determination of Acid Number

The acid number is determined according to DIN EN ISO 2114 (date: June2002), using “method A”. The acid number corresponds to the mass ofpotassium hydroxide in mg required to neutralize 1 g of sample under theconditions specified in DIN EN ISO 2114. The acid number reportedcorresponds here to the total acid number as specified in the DINstandard, and is based on the solids content.

5. Determination of OH Number

The OH number is determined according to DIN 53240-2. The OH groups arereacted by acetylation with an excess of acetic anhydride. The excessacetic anhydride is subsequently split by addition of water to formacetic acid, and the entire acetic acid is back-titrated with ethanolicKOH. The OH number indicates the quantity of KOH in mg that isequivalent to the amount of acetic acid bound in the acetylation of 1 gof sample. The OH number is based on the solids content of the sample.

6. Determination of Number-Average and Weight-Average Molecular Weight

The number-average molecular weight (M_(n)) is determined by gelpermeation chromatography (GPC) according to DIN 55672-1 (March 2016).Besides the number-average molecular weight, this method can also beused to determine the weight-average molecular weight (M_(w)) and alsothe polydispersity d (the ratio of weight-average molecular weight(M_(w)) to number-average molecular weight (M_(n))). Tetrahydrofuran isused as the eluent. The determination is made against polystyrenestandards. The column material consists of styrene-divinylbenzenecopolymers.

WORKING EXAMPLES

The inventive and comparative examples hereinafter serve to elucidatethe invention, but should not be interpreted as imposing any limitation.

With regard to the stated formulation constituents and their quantities,the following should be borne in mind: any reference to a commercialproduct is to exactly that commercial product, irrespective of theparticular principal name selected for the constituent.

1. Release Agent Compositions Used

The release agent compositions Z1 to Z6 are each obtained by homogeneousmixing of the constituents reported in table 1.

TABLE 1 Release agent compositions used Z1 Z2* Z3 Z4* Z5* Z6* Parocryl4085¹⁾ 108.9 201.5 — — 50.38 201.5 Desmophen 670 BA²⁾ 108.9 201.5 — —352.62 201.5 1-Methoxy-2-propyl 201.1 213.0 — — 213.0 213.0 acetateAdditive MI-8010³⁾ — 23.5 — 22.3 23.5 23.5 Borchi Gol OL17⁴⁾ — 9.50 —9.02 9.50 9.50 Silmer OHT Di-10⁵⁾ — 4.50 — 4.27 4.50 4.50 Tinuvin 1130⁶⁾2.43 4.50 — — 4.50 4.50 Butyl acetate 15.7 29.0 — — 29.0 29.0 K-KatXK-651⁷⁾ 7.03 7.03 — — 7.03 7.03 Desmodur N 3800⁸⁾ 154.0 154.0 — — 154.0154.0 Permutex RP-39-525⁹⁾ — — 763.2 727.6 — — Permutex XR-5577¹⁰⁾ — —84.8 84.8 — — Color base BF¹¹⁾ — — — — — 169.6 *used in the process ofthe invention ¹⁾hydroxyl-functional poly(meth)acrylate having a hydroxylnumber of 82.5 mg KOH/g, an acid number of 10 mg KOH/g, M_(n) about 6800g/mol, M_(w) about 17 000 g/mol (BASF SE), ²⁾polyester polyol having ahydroxyl number of 115 mg KOH/g and a hydroxyl functionality of about3.5 (Covestro), ³⁾mixture of compounds of the formulaR¹—(C═O)_(r)—O—(AO)_(s)—R², composed of (a) R¹ = mixture of saturatedand unsaturated hydrocarbon radicals having 12 to 22 carbon atoms, r =0, AO = mixture of primarily ethylene oxide units and a few propyleneoxide units, and R² = H (M_(n) ≈ 650 g/mol); and (b) R¹ = unsaturatedhydrocarbon radical having 21 carbon atoms, s = 0, and R² = H (MünchChemie International GmbH), ⁴⁾polyether-modified methylpolysiloxane(Borchers GmbH), ⁵⁾hydroxy-modified polysiloxane of the formula (III)with the above-recited radicals (Siltec GmbH & Co. KG), ⁶⁾UV absorber A8(BASF Corporation), ⁷⁾bismuth neodecanoate (King Industries),⁸⁾hexamethylene diisocyanate trimer of isocyanurate type with an NCOcontent of 11.0 wt % (Covestro), ⁹⁾aqueous polyurethane dispersion (fromStahl Holdings B.V.), ¹⁰⁾aqueous dispersion of a polycarbodiimide (fromStahl Holdings B.V.), ¹¹⁾color base BF is selected from 55-M 1 1L EffectAdditive, 55-A 098 0.5L stone white, 55-M 141 0.5L yellow, 55-M 306 1Lrust red, 55-A 556 1L ocean blue 2, 55-A 640 1L blue-green, 55-A 974 1Ltinting black, 55-M 99-21 1.0L crystal silver coarse, 55-M 800 1L pearlred-brown.

2. Determination of Adhesive Force of the Release Agent Composition onthe Surface of a Molding Tool

The adhesive force is determined as described above. The results arereproduced in table 2.

TABLE 2 Adhesive force of the release agent compositions on a moldingtool Adhesive force [N] Z1  5** Aqueous release agent WT¹⁾ + Z1 1.6 Z2*0.5 Aqueous release agent WT¹⁾ + Z2  0.15 Z3 4.9 Aqueous release agentWT¹⁾ + Z3 0.9 Z4* 0.6 Aqueous release agent WT¹⁾ + Z4 0.1 *used in theprocess of the invention **delamination ¹⁾Acmosil 36-5645-19 (emulsionof polysiloxanes and other active ingredients in water)

Composition Z1, not used inventively, could not be separated from themolding tool, since the adhesive tape underwent delamination at 5newtons. If additionally, prior to the application of the compositionZ1, an external release agent (aqueous release agent WT) was applied,there was a marked improvement in the releaseability. The inventivelyused compositions Z2 and Z4 exhibit high demoldability even without theuse of an additional, external release agent, the demoldability achievedin fact being better than on combination of the compositions Z1 and Z3with the external release agent (WT). The demoldability of theinventively used compositions Z2 and Z4 can be improved further throughthe use of an additional, external release agent (aqueous release agentWT). Furthermore, the addition of the at least one color base BF doesnot lead to an increase in the adhesive force, and so the readydemoldability of the composition is not adversely affected by thepigmentation (cf. compositions Z2 and Z6).

3. Determination of Further-Processing Time

The further-processing time is determined as described above. Theresults are reproduced in table 3.

TABLE 3 Further-processing time of release agent compositionsFurther-processing time [s] Z1 30 Z2* 25 Z3 85 Z4* 30 *used in theprocess of the invention

In table 3 it is apparent that the inventively used compositions Z2 andZ4 have a lower flashing time than the noninventive compositions Z1 andZ3. Moreover, adding the color base BF has no adverse effect on theflashing time (cf. compositions Z2 and Z6). These short flashing timespermit short operating times for process step (B) and hence an efficientprocess regime.

4. Production and Testing of Coated Components

4.1 Production of Coated Components

The release agent compositions Z1 to Z6 were each manually appliedpneumatically (SATA Jet 4000 B HVLP with nozzle 1.0) to the surface of amolding tool in the form of panels (the mold consists of an aluminumalloy; panel size: 200 mm×200 mm×20 mm, unstructured) (process step(A)). The molding temperature was 55° C. or 65° C. The coating agentlayers were then flashed (flashing time: 20 to 90 s; dry film thickness:about 80 μm (by light microscopy)) (process step (B)).

After the flashing operation, a polyester-based polyurethane foam systemwas injected (process step (D)). This system is obtainable by mixing anA component (containing 100 wt % of polyol mixture 270/40¹⁾ and also10.6 wt % of Elastopan S 7429/155 catalyst²⁾) with a B component(containing Iso 187/68³⁾) in a ratio of 100:84. The foam density is 280to 320 kg/m³. ¹ Polyester polyol mixture having an OH number of 51 mgKOH/g (BASF Italia S.p.A.)² Isocyanate based on 4,4′-diphenylmethanediisocyanate, with an NCO content of 18.7% (BASF Italia S.p.A.)³ Mixtureof aliphatic tertiary amines, glycols, and stabilizers, having a watercontent of 3.9 wt % (BASF Italia S.p.A.)

After closing of the molding tools (process step (E)), crosslinking orcuring of the layer of separating material took place and also theformation of the polyurethane foam over a period of 4 minutes in theclosed mold at 55° C. or 65° C. (process step (F)).

After the 4-minute cure time had elapsed, the molds were opened (processstep (H)). The coated foam material could be manually removed from theopened tool (process step (I)) easily and completely without assistants.However, only the surface of the components produced using thecompositions Z2, Z4, Z5 and Z6 (inventive) meets the mattness requiredin the footwear industry. The surface of the components produced usingthe compositions Z1 and Z3 (not inventive) is very shiny.

4.2 Ross Flex Test

Using the components produced above, the Ross flex test according toASTM D1052:2009 was carried out, with a flex angle of 60°. The test wascarried out in each case over 100 000 cycles, with the components beinginspected after 50 000 cycles and then after each further 10 000 cyclesfor the presence of damage to the surface of the coating.

Even after 100 000 cycles, the components coated by the process of theinvention did not show any surface damage. Accordingly, the coatingsachieved by this process not only lead to outstanding demoldability ofthe components after their production, but also exhibit high adhesion tothe components and high flexibility. The coating, therefore, is alsoextremely robust and therefore does not lead to stress whitening, of thekind occurring in the vacuum foil process.

4.3 Rub Fastness

The rub fastness of the component produced using the release agentcomposition Z6 was tested on the basis of DIN EN ISO 11640:2017-05. Forthis purpose, the respective component was clamped into an SDL AtlasCrockmeter. A commercial abrasive paper of grade P280 was used to rubthe lacquered side of the component, with a pressing force of 9 N, for25 back-and-forth strokes, with a stroke length of 5 cm. The coloredresidue on the abrasive paper and also the surface of the coating werethen inspected. While the abrasive paper did have small residues of thecoating, there was no visible damage to the coating. The process of theinvention, accordingly, leads to coatings which exhibit good rubfastness.

4.4 Migration Fastness

To investigate the migration behavior of the pigments under pressure,the 1-NOVO lacquer system was investigated in accordance with DIN EN ISO15701:2015-07. In this case, the lacquered side of the component coatedwith the release agent composition Z6 was covered with a PVC film (to ENISO 15701) from James Heal. The component and the PVC film were clampedbetween two glass plates in a James Heal Perspirometer and weighted witha weight of 4.5 kg. The Perspirometer was subsequently stored at 50° C.for 16 hours. At the end of the storage time, the experimental set-upwas dismantled again and the PVC film was inspected for discoloration.With the component tested, there was no discoloration of the PVC film.The migration fastness of the coated component is therefore high.

4.5 Accuracy of Hue, Intensity of Hue

The accuracy and the intensity of hue of a component B1 (coated withpigmented release agent composition Z6, unpigmented foam system) wasassessed visually with the intensity of hue of a component B2 (coatedwith unpigmented release agent composition Z2, blue-pigmented foamsystem). The results obtained were as follows (rating 1: accuracy of huecomparable with OEM vehicle finishing, viz. very high hue intensity,rating 2: accuracy of hue poorer than for OEM vehicle finishing, viz.high hue intensity, rating 3: accuracy of hue significantly poorer thanfor OEM vehicle finishing, viz. low intensity of hue).

Component Accuracy of hue Intensity of hue B1 3 3 B2 1 1

As is evident from the table above, the coating of components by theprocess of the invention with pigmented release agent compositions(component B1) leads to greater accuracy of hue and intensity of huethan the pigmentation of the foam material (component B2).

4.6 Compatibility

To determine the compatibility of the coating material compositions withfoam compositions used in the production of components, components wereproduced as described under 4.1. The components were produced usingrelease agent composition Z2, a wax-based release agent (Münch Chemie),and a silicone-based release agent (Münch Chemie). The compatibility ofthe release agent with the foam system used to produce the component wasassessed visually, with incompatibility being manifested by bulges andindentations in the foam. The results obtained were as follows (rating1: very good compatibility, rating 2: good compatibility, rating 3:satisfactory compatibility, rating 4: adequate compatibility).

TABLE 4 Compatibility of the release agent compositions ComponentRelease agent composition Compatibility B1* Z2 1 B2 wax-based releaseagent 3 B3 silicone-based release agent 4 *obtainable by inventiveprocess

From table 4 it is apparent that the release agent composition Z2 usedin the inventive process exhibits very good compatibility with the foamsystem used for producing the components. The inventively producedcomponent (B1) has no bulges or indentations. In contrast, thenoninventively produced components (B2, B3) have bulges andindentations, owing to the merely satisfactory or adequate compatibilitybetween release agent and foam system.

4.7 Effect of the Release Agent Composition on the Flow Properties ofthe Composition Used for Producing Components

To determine the effect of the release agent compositions on the foamcompositions used for producing components, components were produced asdescribed under 4.1. The components were produced using the releaseagent composition Z2 (inventive component B1) and also an aqueousrelease agent (MP6032-5, Münch Chemie) (noninventive component B2). Themolding tools used was a molding tool with simple geometry, a moldingtool with more complex geometry, in footwear sole form, and a moldingtool with angled geometry, including struts just a few millimeters wide.The demolding and the filling of the molding tool by the foam systemwere each assessed visually. The results obtained were as follows(rating 1: very good demolding or very high improvement in the flowproperties, rating 2: good demolding or high improvement in the flowproperties, rating 3: satisfactory demolding or minimal defects in thecomponent, rating 4: adequate demolding or high number of defects in thecomponent).

TABLE 5 Effect of the release agent compositions on the flow propertiesof the foam system Effect on flow Molding tool Component Demoldabilityproperties Simple plate B1* 1 1 geometry B2 1 1 Footwear sole B1* 1-2 1B2 2-3 2 Angled geometry B1* 2 1 B2 3-4 3 *obtainable by inventiveprocess

From table 5 it is apparent that with the process of the invention,outstanding demoldability is achieved even when using molding tools ofhighly complex geometry. With the process of the invention, moreover,the flow property of the foam system is improved, and so even narrowcavities in the molding tool can be fully filled with the foamcomposition. This allows the defect-free production of components ofcomplex geometry. Conversely, a noninventive process in the case of morecomplex molding tools leads to poorer demoldability. With this process,moreover, especially in the case of complex molding tools, defects arisedue to the lack of filling of cavities.

1. A manual process for injection molding of coated components, theprocess comprising the following steps in the order indicated: (A)applying a release agent composition to at least one inside of at leastone molding part of a closable molding tool, (B) flashing the releaseagent composition applied in step (A), (C) optionally inserting at leastone material M1 and heating of the molding tool, (D) applying acomposition Z1 into the opened molding tool, (E) manually closing themolding tool, (F) crosslinking the release agent composition and alsothe composition Z1 applied in process step (D), (G) optionally applyingat least one further composition Z2 and crosslinking the composition(s),(H) manually opening the molding tool, (I) manually removing the moldedcoated component, and (J) optionally aftertreating the molded coatedcomponent, wherein the release agent composition comprises: (a) at leastone solvent L, (b) at least one compound of the general formula (I)R¹—(C═O)_(r)—O-(AO)_(s)—R²   (I) in which R¹ is a saturated orunsaturated, aliphatic hydrocarbon radical having 6 to 30 carbon atoms,R² is H, a PO(OH)₂ radical, or the optionally partially phosphatedradical of a monosaccharide or disaccharide, or the optionally partiallyphosphated radical of an alditol, AO stands for one or more alkyleneoxide radicals selected from the group consisting of ethylene oxide,propylene oxide and butylene oxide, r is 0 or 1, and s is 0 to 30; (c)optionally at least one polyether-modified alkylpolysiloxane, (d) atleast one polysiloxane of the general formula (II)R³—Si(R⁴)₂[—O—Si(R⁴)(R⁵)]_(a)—[O—Si(R⁴)₂]_(b)—O—Si(R⁴)₂—R³   (II), inwhich R³ and R⁴, in each case independently of one another, are a methylgroup or a (HO—CH₂)₂—C(CH₂—CH₃)—CH₂—O—(CH₂)₃—. radical, R⁵ is a methylgroup, a is 0 or 1 to 10, and b is 3 to 30; and (e) optionally at leastone binder B.
 2. The process as claimed in claim 1, wherein the releaseagent composition has a viscosity of 10 to 60 s.
 3. The process asclaimed in claim 1, wherein, in the general formula (I), R¹ is asaturated or unsaturated aliphatic hydrocarbon radical having 10 to 24carbon atoms, R² is H, a PO(OH)₂ radical, or the optionally partiallyphosphated radical of a monosaccharide or disaccharide, or theoptionally partially phosphated radical of an alditol, AO stands for oneor more alkylene oxide radicals selected from the group consisting ofethylene oxide and propylene oxide, r is 0 or 1, and s is 0 or 1 to 25.4. The process as claimed in claim 1, wherein the release agentcomposition comprises the at least one compound of the general formula(I) in a total amount of 0.1 to 10 wt % based on the total weight of therelease agent composition.
 5. The process as claimed in claim 1, whereinthe polyether-modified alkylpolysiloxane comprises at least onestructural unit (R⁷)₂(OR⁶)SiO_(1/2) and at least one structural unit(R⁷)₂SiO_(2/2), where R⁶ is an ethylene oxide, propylene oxide, andbutylene oxide group and R⁷ is a C₁-C₁₀ alkyl group.
 6. The process asclaimed in claim 1, characterized in that the release agent compositioncomprises the at least one polyether-modified alkylpolysiloxane in atotal amount of 0 wt % or of 0.1 to 6 wt % based on the total weight ofthe release agent composition.
 7. The process as claimed in claim 1,wherein, in the general formula (II), the radical R³ is a(HO—CH₂)₂—C(CH₂—CH₃)—CH₂—O—(CH₂)₃—. radical, the radical R⁴ is a methylgroup, the radical R⁵ is a methyl group, a is 0, and b is 7 to
 14. 8.The process as claimed in claim 1, wherein the release agent compositioncomprises the at least one polysiloxane of the general formula (II) in atotal amount of 0.1 to 5 wt % based on the total weight of the releaseagent composition.
 9. The process as claimed in claim 1, wherein therelease agent composition comprises the at least one binder B in a totalamount (solids content) of 20 to 50 wt % based on the total weight ofthe composition.
 10. The process as claimed in claim 1, wherein thebinder B is selected from the group consisting of (i)poly(meth)acrylates, (ii) polyurethanes, (iii) polyesters, (iv)polyethers, (v) copolymers in the stated polymers, and (vi) mixturesthereof.
 11. The process as claimed in claim 1, wherein the releaseagent composition is flashed in process step (B) for a period of 20seconds to 120 minutes.
 12. The process as claimed in claim 1, whereinthe composition Z1 applied in process step (D) is a polymer foam. 13.The process as claimed in claim 1, wherein the crosslinking in processstep (F) takes place for a period of 1 to 20 minutes.
 14. The process asclaimed in claim 1, wherein the process comprises a further process stepin which the molding tool, after the removal of the coated component inprocess step (I), is cleaned.
 15. The process as claimed in claim 14,wherein the further process step is carried out after 20 to 100repetitions of process steps (A) to (I).
 16. The process as claimed inclaim 1, wherein the release agent composition comprises the at leastone compound of the general formula (I) in a total amount of 0.5 to 5 wt%, based on the total weight of the release agent composition.
 17. Theprocess as claimed in claim 1, wherein the polyether-modifiedalkylpolysiloxane comprises at least one structural unit(R⁷)₂(OR⁶)SiO_(1/2) and at least one structural unit (R⁷)₂SiO_(2/2),wherein R⁶ is a mixture of ethylene oxide and propylene oxide andbutylene oxide groups, and R⁷ is a methyl group.
 18. The process asclaimed in claim 1, characterized in that the release agent compositioncomprises the at least one polyether-modified alkylpolysiloxane in atotal amount of 0.5 to 4 wt %, based on the total weight of the releaseagent composition.
 19. The process as claimed in claim 1, wherein therelease agent composition comprises the at least one polysiloxane of thegeneral formula (II) in a total amount of 0.5 to 4 wt %, based on thetotal weight of the release agent composition.
 20. The process asclaimed in claim 1, wherein the binder B is selected from the groupconsisting of (i) hydroxy-functional and/or carboxylate-functionaland/or amine-functional poly(meth)acrylates, (ii) hydroxy-functionaland/or carboxylate-functional and/or amine-functional polyurethanes,(iii) polyester polyols, (iv) polyether polyols, (v) copolymers in thestated polymers, and (vi) mixtures thereof.